US20150020993A1

US 2015.
0020993A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2015/0020993 A1
Amendola et al. (43) Pub. Date: Jan. 22, 2015
(54) MECHANICAL-CHEMICAL ENERGY Publication Classification
STORAGE
(51) Int. Cl.
(71) Applicant: Eos Energy Storage, LLC, Edison, NJ F28D 20/00 (2006.01)
(US) C09K 5/16 (2006.01)
(52) U.S. Cl.
(72) Inventors: Steven Amendola, Easton, PA (US); CPC ................ F28D 20/003 (2013.01); C09K 5/16
Tibor Kalnoki-Kis, Westlake, OH (US) (2013.01)
USPC ............................................................ 165/10
(21) Appl. No.: 14/329,201 (57) ABSTRACT
This invention generally relates to mechanical-chemical
(22) Filed: Jul. 11, 2014 energy storage. In particular, the invention relates to a
mechanical-chemical energy storage system that stores
Related U.S. Application Data
energy by simultaneously compressing a gas to a higher
enthalpy state and recovering the heat of compression by
(60) Provisional application No. 61/844.914, filed on Jul. driving a somewhat reversible chemical reaction. The heat
11, 2013, provisional application No. 61/968,450, energy in the chemical reaction is then recovered while the
filed on Mar. 21, 2014. gas is expanding to a lower enthalpy state.
EXPANSION 8, ABSORPTION
HIGH PRESSURE
HEAT REACTORVESSEL
EXCHANGER (ABSORPTION)
(EXPANSION)
CONTROL
METERNALVE
Patent Application Publication Jan. 22, 2015 Sheet 1 of 17 US 2015/0020993 A1
FIG. 2
FIG. 4
202
Working
Fluid
Storage
Tank
Working
Fluid
Storage
Tank
##
540
530
(TIL| |(1| |(L| |

FIG. 7A
D
(C
D
510
FIG. 7B
| | | | | No.s ||
|
FIG. 8A
884
FIG, 8B
OMPZ, 60°C
107
6 oMEA(Jou, 60C)
10' HAMEA(Jou,40C) - - - - - - - - - - - - - - - - - - - -- w - - - - - - - - - - - - cers - - - - - - - - - - - - - - -
105 OMEA (exp, 40C) - - - -- -- -- - --- - - - - Y - - - - - - a raw- - - - - - - - V - - - - - as - - - - -
AMEA (exp, 40C)

S 10" | EMEAPZ (exp,40C)
NMEAVPZ (exp, 60C)
-- -- Y ---- - - - -- - -- - r ------- - - - - -- - - --
n 10 ele - --- ---- - - - - -- -- - - -- -- --a- ----- ---- - - --
10 ------------------ - or - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
101 ...e4.
100
O 0.2 0.4 0.6 0.8 1
Loading (mol CO/molamine)
FIG. 9
- MEAVPZ(pred. 60C)
- - - MEAJPZ(pred. 40C)
X MEA (Jou, 60C)
10
N MEA (exp. 60C) :
E MEAJPZ(exp. 60C):
A MEA (Jou. 40C) :
OMEA (exp. 40C)
5s O MEAPZ(exp,40C)
A
O
Q 10'-
8
O 0.2 0.4 0.6 0.8 1

Loading (mol CO/mol amine)
FIG. 10
40
-O-MOF.177
-O-RMOF-1
35-A-IRMOF-6
-A-RMOF-3
30 -- IRMOF-11
-O-CU(BTC)
-O-MOF-74
25--O-MOF-505
-V-Norit RB2
20
15
HHM
1O a 2E
O 15 30 45
Pressure (bar)
FIG. 11
PUMP
O
WET
COMPRESSED
COINH
Co.
(4)
PUMPO
LEANLIQUID
COINHIHO
REBOLER
SENSIBLE
ENERGY
180°F H.8
LIQUID
RICH
COINHIHO
CEN) (CSR H.84 ER
É65 A6 : CO2
LIQUID
LIQUID
FIG. 13
3. Phase System
COMPRESSION &
&e l
-
FIG. 14A
COMPRESSION
"HEATING"
YCOOLING
LIQUEFACTION
PESEAT
EXCHANGE
FIG. 14B
Throttle & Discharge
HEAT
EXCHANGE
FIG. 14C
EXPANSION & ABSORPTION

HIGH PRESSURE
HEAT REACTORVESSEL
EXCHANGER (ABSORPTION)
(EXPANSION)
POWER
oro FIG. 15A

METERNALVE
DESORPTION & COMPRESSION

HIGH PRESSURE
HEAT s REACTORVESSEL
EXCHANGER (DESORPTION)
(LIQUEFACTION) s
MULTISTAGE
CONTROL
FIG. 15B
METERNALVE
, %29
ZH
? 0,8
@ JO
??
ZH
100
|
80
60
40 FIG. 17A
20
O
0.0 0.2 0.4 0.6 0.8 1.0
CO, Loading (mol CO/mol NH)
120
100
80
60
40 FIG. 17B
20
O
0.0 0.2 0.4 0.6 0.8 1.0
160
140
120
100
80
60 FIG. 17C
40
20
O
0.0 0.2 0.4 0.6 0.8 1.0
350
3OO
25O
| 2O O
150
100
5O
O
O 0.02 0.04 0.06 0.08 0.1 0, 12 0.14 0.16 0.18
x (wt % CO2 dissolved in MEA)
FIG. 18
60
50
Expander Out P 100psiao
a. 0Expander Qut P200 psia.
S 40 AExpander Outlet P 300 psia
s (0
a 30 0.
0. AA
s 00 AA
2 0 AAAA'
i 20 AAA
10
O
O 50 100 150 200 250 300 350
Expander Inlet T(F)
FIG. 19
120
100
s
80
is5 0
0
0 0
()
SD 0 A A
5. 40
O
E A A
A A
20 Compressor in P 100 psia
0 Compressor in P200 psia
A Compressor in P300 psia
O
-50 O 50 100 150 200
Compressor Inlet T(F)
FIG. 20
70
0.
60
0 1-Stage Comp
2-Stage Comp
A 3-Stage Comp
10
-20 30 80 130 180

Compressor Inlet T(F)
FIG 21
1
0.9
0.8
0.7 AA
0.6 AA (0
0.5
0.4 00
0.3 0 1-Stage Exp, 1-Stage Comp
0.2 2-Stage EXp, 2-Stage Comp
0.1 A 2-Stage Exp, 3-Stage Comp
O
O 50 100 150 200 250 300 350
Expander Inlet T(F)
FIG. 22
0.5- -() 0
- - Y -
0.4
0.3
0.2
0 1-Stage Exp, 1-Stage Comp Comp
1-Stage Exp, 1-Stage Comp Comp,
Pump to 1400 psia
150 17O 190 210 230 250 270 290 31 0 330
Expander Inlet T(F)
FIG. 23
US 2015/0020993 A1 Jan. 22, 2015
MECHANCAL-CHEMICAL ENERGY stored energy is only recovered if it is also desired to burn

STORAGE natural gas to run the gas turbine to create energy.
0006 Traditional efforts to recover this heat from com
CROSS REFERENCE TO RELATED pression involve storing the heat of compression in a medium
APPLICATION (such as water), as sensible heat, which simply raises the
0001. This U.S. application claims the benefit of U.S. pro temperature of the water. This warm water is stored in an
visional application Nos. 61/844.914, filed on Jul. 11, 2013, insulated tank until the energy is required to heat the working
and 61/968,450, filed on Mar. 21, 2014. Each of these docu fluid while expanding it to recover that energy. However,
ments is incorporated herein in its entirety. warm water has reduced energy dense medium. Furthermore,
the low temperature gradients present engineering challenges
FIELD OF THE INVENTION to achieve high power output that requires high rates of heat
transfer over a low temperature gradient. Problems also exist
0002 This invention generally relates to mechanical due to heat from the stored water escaping from the insulated
chemical energy storage. In particular, the invention relates to tank giving the system an apparent 'self-discharge, analo
a mechanical-chemical energy storage system that stores gous to electrochemical batteries.
energy by simultaneously compressing a gas to a higher
enthalpy state and recovering the heat of compression by SUMMARY OF THE INVENTION
driving a somewhat reversible chemical reaction. The heat
energy in the chemical reaction is then recovered while the 0007. The present invention solves one or more of the
gas is expanding to a lower enthalpy state. problems described above by combining the high energy
density of a liquefied gas, the high RTE of operating near
BACKGROUND ambient temperatures, and the ability to achieve high power
0003 Energy storage is vitally important for the stability densities by generating the heat required for expansion when
of the electric grid as it relies more on “non-dispatchable' it is needed rather than storing heat for use at Some other time.
Sources of power Such as Solar and wind. Additionally, there 0008. In one aspect, the present invention provides a
are many applications where long term power may be needed method for storing energy comprising: providing an absor
apart from any grid such as in military or emergency situa bent reservoir containing a working fluid that is chemically
tions. Currently, the most common solutions are lead-acid absorbed by an absorbent; desorbing the working fluid from
batteries and diesel generators. The shortcomings of these the absorbent in an endothermic process; and condensing the
systems are well known. Most electrochemical batteries show working fluid in an exothermic process and transferring the
a significant degradation in performance as they are dis condensed working fluid to a working fluid reservoir under
charged. This is evidenced by reduced Voltage output and pressure; wherein at least some of the heat generated during
reduced maximum currents observed during the discharge of the condensing step is recycled to drive the desorbing step.
the battery. Batteries also tend to be less efficient and have 0009. Another aspect of the present invention provides a
reduced service lives when run at greater depths of discharge. method for storing energy comprising providing an absorbent
0004. There is increased interest in using stored mechani reservoir containing a working fluid that is chemically
cal energy to ultimately serve as electrical energy storage for absorbed by an absorbent; desorbing the working fluid from
grid type applications. This interest is based in part on the the absorbent in an endothermic process; and condensing the
robust nature and highly developed state of the art of working fluid in an exothermic process and transferring the
mechanical power generation equipment, which is economi condensed working fluid to a working fluid reservoir under
cal and Scalable. In general, most energy storage schemes pressure; wherein at least some of the heat generated during
compress a working fluid to high pressures or liquefy the the condensing step is recycled to drive the desorbing step.
working fluid by compression and/or temperature reduction. 0010. In some implementations, the working fluid com
Alternately, a series of heat pumps (often coupled to genera prises carbon dioxide, ammonia, nitrous oxide, air, or water.
tors and/or other heat Sources) indirectly accomplish this For example, the working fluid comprises carbon dioxide or
same goal where working fluid(s) is/are cycled with the com ammonia. In some instances, the working fluid comprises
bination of heat pumps. This alternative has higher cost asso ammonia. In other instances, the working fluid comprises
ciated with extra machinery. In general, to get higher recov nitrous oxide.
eries (efficiencies that we will refer to as “round trip 0011. In some implementations, the absorbent comprises
efficiency” or “RTE) requires more “stages” to recover an organic amine, an inorganic base, an activated carbon,
energy, and each additional stage is met with reduced energy silica gel, a Zeolite, a metal organic framework, or any com
recovery. Thus, these systems require increased capital to bination thereof. For example, the absorbent comprises an
achieve high RTE after more than two stages. organic amine selected from monoethanolamine, piperazine,
0005. Other conventional energy storage systems store ammonia, morpholine, diethanolamine, diglycolamine,
energy by compressing a gas to high pressure. Depending on diisopropanolamine, triethanolamine, dibutylamine, methyl
the physical properties (critical temperature) of the gas, it diethanolamine, diethylenetriamine, or any combination
may liquefy. During this compression process, heat is gener thereof. In other examples, the absorbent comprises a metal
ated and much of this heat is generally lost, which results in halide Salt, a mild acid, water, activated carbon, silica gel, a
reduced RTEs. This is a common problem in compressed air Zeolite, or metal organic framework. And, in some examples,
energy storage (CAES). The RTE of conventional systems is the absorbent comprises a food oil, silicone oil, activated
around 50%. RTEs of these systems are limited due to the use carbon, silica gel, Zeolite, or metal organic framework.
of assisting gas turbines during operation to increase the 0012. In some implementations, the heat generated from
overall efficiency of that device. Assisting gas turbines are not the condensing step is recycled to drive the desorbing step
a true energy storage systems, but act as a hybrid, wherein using a heat exchanger.
US 2015/0020993 A1 Jan. 22, 2015
0013 Some implementations further comprise compress 0027. In other implementations, the compressing step
ing the working fluid using a reversible turbine. comprises a two-stage compression process.
0014 Some implementations further comprise compress 0028. In some implementations, the working fluid is
ing the working fluid and storing the working fluid in the expanded to a pressure of from about 0.1 bar to 10 bar.
working fluid reservoir in a liquid State, a critical state, or a 0029. In other implementations, the working fluid is
trans-critical state. stored at ambient temperature.
0015. In some implementations, the working fluid is com 0030 Some implementations further comprise heating the
pressed to and stored at a pressure of from about 1 bar to about working fluid prior to expansion using an external heat
100 bar. SOUC.
0016 Some implementations further comprise a second 0031. Some implementations further comprise directing
compression step after the first compression. the flow of the working fluid a first direction during charging,
0017. In some implementations, the working fluid is and reversing the flow of the direction of the working fluid
expanded to a pressure of from about 0.1 bar to 10 bar. during discharging.
0018. In some implementations, the working fluid is 0032. Another aspect of the present invention provides an
stored at ambient temperature. energy storage system comprising a working fluid reservoir
0019. Some implementations further comprise heating the containing compressed working fluid; an expander that flu
working fluid prior to expansion using an external heat idly communicates with the working fluid reservoir and is
SOUC. configured to expand the working fluid; an absorbent storage
0020. Another aspect of the present invention provides a reservoir containing an absorbent, wherein the absorbent res
method of charging and discharging an energy storage system ervoir fluidly communicates with the expander and is config
comprising charging the System comprising providing an ured to receive and absorb the expanded working fluid; a first
absorbent storage tank containing a working fluid that is heat exchanger that thermally communicates with the absor
chemically absorbed by an absorbent; desorbing the working bent reservoir and is configured to transfer heat generated by
fluid from the absorbent in an endothermic process; condens the absorption of the working fluid by the absorbent to the
ing the working fluid in an exothermic process and transfer working fluid during the discharge of the system; a pressure
ring the condensed working fluid to a working fluid reservoir release mechanism configured to reduce pressure in the
under pressure; recycling heat generated during the condens absorbent reservoir, and a compressor that fluidly communi
ing step to drive the desorbing step; and storing the working cates with the absorbent reservoir and fluidly communicates
fluid in a working fluid reservoir under pressure; and dis with the working fluid reservoir and is configured to compress
charging the system comprising expanding the working fluid; the working fluid that desorbs from the absorbent; and a
chemically absorbing the working fluid with the absorbent in second heat exchanger in thermal communication with the
the absorbent reservoir in an exothermic process; recycling working fluid in the compressor, in thermal communication
heat generated during the absorption reaction to drive the with the absorbent and working fluid in the absorbent storage
expanding step; and storing the absorbent and the absorbed tank, and configured to transfer heat that is generated by the
working fluid in the absorbent reservoir. compression of the working fluid, to the absorbent and work
0021. In some implementations, the working fluid com ing fluid in the absorbent storage tank.
prises carbon dioxide, ammonia, nitrous oxide, air, or water. 0033. In some embodiments, the working fluid comprises
For example, the working fluid comprises carbon dioxide. In carbon dioxide, ammonia, nitrous oxide, air, or water.
another example, the working fluid comprises ammonia. And, 0034. In some embodiments, the absorbent comprises an
in Some examples, the working fluid comprises nitrous oxide. organic amine, inorganic base, activated carbon, silica gel.
0022. In some implementations, the absorbent comprises Zeolite, or metal organic framework. For example, the absor
an organic amine, inorganic base, activated carbon, silica gel. bent comprises an organic amine selected from monoethano
Zeolite, or metal organic framework. For example, the absor lamine, piperazine, ammonia, morpholine, diethanolamine,
bent comprises an organic amine selected from monoethano diglycolamine, diisopropanolamine, triethanolamine, dibu
lamine, piperazine, ammonia, morpholine, diethanolamine, tylamine, methyl-diethanolamine, or diethylenetriamine. In
diglycolamine, diisopropanolamine, triethanolamine, dibu other examples, the absorbent comprises a metal halide salt,
tylamine, methyl-diethanolamine, or diethylenetriamine. In mild acid, water, activated carbon, silica gel, Zeolite, or metal
Some examples, the absorbent comprises a metal halide salt, organic framework. And, in Some examples, the absorbent
mild acid, water, activated carbon, silica gel, Zeolite, or metal comprises a food oil, silicone oil, activated carbon, silica gel.
organic framework. And, in Some examples, the absorbent Zeolite, or metal organic framework.
comprises a food oil, silicone oil, activated carbon, silica gel. 0035. In some embodiments, the compressor and
Zeolite, or metal organic framework. expander comprise a reversible turbine.
0023. In some implementations, the heat generated during 0036. In other embodiments, the compressor comprises a
the condensing step is recycled drive the desorbing step using
a heat exchanger. turbine, piston, radial reaction turbine.
0024. In other implementations, the working fluid is com 0037. In some embodiments, the expander comprises a
pressed by a reversible turbine. turbine, piston, or turbo-expander.
0025. Some implementations further comprise compress 0038. Some embodiments further comprise an electrical
ing the working fluid and storing the working fluid in the generator connected to the expander.
working fluid reservoir in a liquid State, a critical state, or a 0039. Some embodiments further comprise a motor con
trans-critical state. nected to the compressor.
0026. In some implementations, the working fluid is com 0040 Some embodiments further comprise an external
pressed to and stored at a pressure of from about 1 bar to about heat source, in thermal communication with the expanded
100 bar. working fluid.
US 2015/0020993 A1 Jan. 22, 2015
0041. Some embodiments further comprising a controller fluid that desorbs from the absorbent; and a second heat
connected to the compressor, expander, pressure release exchanger in thermal communication with the working fluid
mechanism, absorbent storage tank, and working fluid Stor in the compressor, in thermal communication with the absor
age tank. bent and working fluid in the absorbent storage tank, and
0042. In some embodiments, the first heat exchanger and configured to transfer heat that is generated by the compres
second heat exchanger each comprise high Surface area fin sion of the working fluid, to the absorbent and working fluid
shaped structures within the absorbent storage tank. in the absorbent storage tank.
0043. Some embodiments further comprise one or more
additional compressors, fluidly connected to and positioned BRIEF DESCRIPTION OF THE DRAWINGS
between the first compressor and the working fluid storage 0.052 FIG. 1 is a schematic diagram of an embodiment of
tank. the mechanical-chemical energy storage system of the
0044 Some embodiments further comprise one or more present invention being charged.
additional expanders, fluidly connected to and positioned 0053 FIG. 2 is a schematic diagram of an embodiment of
between the first expander and the absorbent storage tank. the mechanical-chemical energy storage system of the
0045. In some embodiments, the pressure release mecha present invention being discharged.
nism is a valve. 0054 FIG. 3 is a schematic diagram of an embodiment of
0046. Some embodiments further comprise a pump and a the mechanical-chemical energy storage system of the
sprayer that each fluidly communicates with each other and present invention being discharged.
with the absorbent storage tank, wherein the pump pumps the 0055 FIG. 4 is a schematic diagram of an embodiment of
absorbent and absorbed working fluid to the sprayer and the the mechanical-chemical energy storage system of the
sprayer sprays the fluid back into the absorbent storage tank. present invention being charged.
For example, the sprayer sprays the absorbent over a heat 0056 FIG. 5A is a schematic of an embodiment of the
exchanger with high Surface area fin-shaped structures within mechanical-chemical energy storage system of the present
the absorbent storage tank. invention being discharged.
0047. Some embodiments further comprise a separator 0057 FIG. 5B is a schematic of an embodiment of the
that fluidly communicates with the absorbent storage tank mechanical-chemical energy storage system of the present
and the compressor. invention being charged.
0048. In some embodiments, the separator is a centrifugal 0.058 FIG. 6A is a schematic of an embodiment of a
or cyclonic separator. mechanical-chemical energy storage System being dis
0049. In some embodiments, the separator is a demister or charged.
a filter. 0059 FIG. 6B is a schematic of an embodiment of a
0050. Another aspect of the invention provides a method mechanical-chemical energy storage system being charged.
of charging and discharging an energy storage system com 0060 FIG. 7A is an illustration of a top view of a heat
prising: (i) charging the system comprising: providing an exchanger in accordance with the present invention having
absorbent tank containing a working fluid that is chemically high Surface area fin-shaped structures ("fins') integrated
absorbed by an absorbent; desorbing the working fluid from with an absorbent storage tank.
the absorbent in an endothermic process; condensing the 0061 FIG. 7B is an illustration of a side view of a heat
working fluid in an exothermic process and transferring the exchanger in accordance with the present invention having
condensed working fluid to a working fluid reservoir under high Surface area fin-shaped structures ("fins') integrated
pressure; recycling heat generated during the condensing step with an absorbent storage tank.
to drive the desorbing step; and storing the working fluid in a 0062 FIG. 8A is a side view of a mechanical-chemical
working fluid reservoir under pressure; and (ii) discharging energy storage system according to the present invention.
the system comprising: expanding the working fluid; chemi 0063 FIG. 8B is a top view of a mechanical-chemical
cally absorbing the working fluid with the absorbent in the energy storage system according to the present invention.
absorbent reservoir in an exothermic process; recycling heat 0064 FIG. 9 is a graph of CO working fluid pressure
generated during the absorption reaction to drive the expand Versus the concentration of CO in an amine generated using
ing step; and storing the absorbent and the absorbed working a computer model of an embodiment of the present invention.
fluid in the absorbent reservoir. 0065 FIG. 10 is a graph of CO working fluid partial
0051. Another aspect of the invention provides an energy pressure in a CO/amine solution versus the concentration of
storage system comprising: a working fluid reservoir contain CO in an amine generated using a computer model of an
ing compressed working fluid; an expander that fluidly com embodiment of the present invention.
municates with the working fluid reservoir and is configured 0.066 FIG. 11 is a graph of uptake of several metal organic
to expand the working fluid; an absorbent storage reservoir frameworks and activated carbons as a function of pressure,
containing an absorbent, wherein the absorbent reservoir flu generated using a computer model of embodiments of the
idly communicates with the expander and is configured to present invention.
receive and absorb the expanded working fluid; a first heat 0067 FIG. 12 is a graph offlux versus pressure of working
exchanger that thermally communicates with the absorbent fluid CO2 generated using a computer model of an embodi
reservoir and is configured to transfer heat generated by the ment of the present invention.
absorption of the working fluid by the absorbent to the work 0068 FIG. 13 is a schematic process flow diagram using
ing fluid during the discharge of the system; a pressure release separate working fluid and adsorption/desorption streams in
mechanism configured to reduce pressure in the absorbent accordance with the present invention.
reservoir, a compressor that fluidly communicates with the 0069 FIGS. 14A-14C are schematics of the processes
absorbent reservoir and fluidly communicates with the work involved in the charge, discharge, and throttle cycles in accor
ing fluid reservoir and is configured to compress the working dance with the present invention.
US 2015/0020993 A1 Jan. 22, 2015
0070 FIGS. 15A and 15B are schematics of a mechanical ible chemical reaction with an absorbent that releases heat
chemical energy storage system according to the present (exothermic). The heat is captured, for example by a heat
invention. exchanger, and the heat is transferred to the compressed
0071 FIG. 16 is a schematic of the processes involved in working fluid that has yet to undergo expansion. This trans
the charge and discharge of a mechanical-chemical energy ferred heat beneficially increases the enthalpy of the working
storage system according to the present invention. fluid prior to expansion, thus allowing for greater energy
0072 FIG. 17A is a graph showing differential enthalpies production. The process can continue until the compressed
of absorption of carbon dioxide in 2.5 wt % aqueous ammonia working fluid storage tank is empty.
in a reactor at 40°C. I0085. During the charge process, the absorbed working
0073 FIG. 17B is a graph showing differential enthalpies fluid is desorbed through an endothermic reaction that is
of absorption of carbon dioxide in 2.5 wt % aqueous ammonia driven by a reduction in the pressure of the working fluid and
in a reactor at 60° C. absorbent. Energy is provided to a compression device that
0074 FIG. 17C is a graph showing differential enthalpies compresses the working fluid to a liquid or Supercritical state
of absorption of carbon dioxide in 2.5 wt % aqueous ammonia and is stored in a storage tank. Heat from the compression
in a reactor at 80° C. process is captured and transferred to drive the endothermic
0075 FIG. 18 is a graph of temperature of the absorbed desorption reaction. The process can continue until all of the
CO/MEA mixture as a function of the weight percent of CO working fluid has been desorbed and stored in the storage
absorbed in MEA, generated using a computer model of an tank.
embodiment of the present invention. I0086. The systems and methods of the present invention
0076 FIG. 19 is a graph of expanderpower as a function of have some or all of the following properties:
inlet temperature at several outlet pressures, generated using 0.087 High RTE.
a computer model of an embodiment of the present invention. 0088 A high energy density due to high density mate
0077 FIG.20 is a graph of compressor power as a function rial forms.
of inlet temperature at several inlet pressures, generated using 0089. A closed cycle device not limited to air or nitro
a computer model of an embodiment of the present invention. gen as a working fluid.
0078 FIG. 21 is a graph of net power as a function of inlet 0090 Scalable using existing equipment for powergen
temperature to the compressor for one-, two-, and three-stage eration and handling of liquefied gases.
compressions, generated using a computer model of an 0.091 Energy and power performance specifications
embodiment of the present invention. can be designed independently of each other.
0079 FIG. 22 is a graph of RTE as a function of inlet 0092 Very low cost.
temperature to the expander for one-, two-, and three-stage (0.093 Extremely, long cycle life.
compressions, generated using a computer model of an 0094. No self-discharge as heat is never stored as sen
embodiment of the present invention. sible heat but only as chemical potential.
0080 FIG. 23 is a graph of RTE as a function of expander 0.095 Ability to use waste heat or extract heat from the
inlet temperature, generated using a computer model of an atmosphere to achieve even greater energy conversions.
embodiment of the present invention.
0081. These figures are provided by way of example and I. DEFINITIONS
are not intended to limit the scope of the invention. (0096. For brevity, from here on we will refer to the “grid”
DETAILED DESCRIPTION as being any application or Solution for which the invention is
suitable. We shall also refer to the operation of any of these
0082 In one aspect, the invention relates to the storage and systems in which energy is put into the device to charge it, as
delivery of energy as mechanical energy. In as much as “charging or “recharging”. Consistent with this definition,
mechanical and electrical energy are easily interchanged at when energy is taken out of the device it is referred to as
high efficiencies by motors and generators, the system may “discharging”. Any cycle of charge (partial or full) and dis
also function as a “battery” even though there are no electro charge (partial or full) will simply be referred to as a “cycle'.
chemical reactions involved in the storage of energy by this 0097. As used herein, “chemical absorption” refers to
invention notwithstanding the incidental use of conventional absorption using a chemical bond of a covalent pair to form
batteries for some system functions. either a solution or compound.
0083. In another aspect, the invention relates to a chemical 0098. As used herein, the term “tank” and “reservoir are
and thermodynamic system for energy storage. Energy is used interchangeably to refer to a storage chamber.
stored and released using distinct charge and discharge pro 0099. As used herein, "desorption' is a process that is the
cesses. This system simultaneously compresses a working inverse of absorption whereby some, or all, of an absorbed
fluid to a higher enthalpy state and recovers the heat of com Substance is released. Specifically, desorption is the process
pression by driving a reversible chemical reaction. The com by which the molecules of a covalent pair are separated from
pressed fluid is then expanded to a lower enthalpy state and each other in order to form, or reconstitute the original, prior
chemically absorbed, driving the reverse exothermic reac to absorption, covalent pair.
tion, from which heat can be supplied to increase the expan 0100 For brevity, embodiments of the invention may be
sion efficiency. described as involving either an “absorption” or "adsorption'
0084. During the discharge process, compressed working process. It will be understood to the reader that either process
fluid (e.g., liquefied or Supercritical gas) from a storage tank may be used in the embodiments of the invention depending
is expanded through an expansion device such as a turbine, on the choice of materials. Similarly, the terms “absorption
piston, or nozzle, thereby generating power. The expansion agent”, “absorbent, or “sorbent are used interchangeably
results in cooling of the working fluid. The expanded working and may each refer to either a liquid or a solid agent that can
fluid (gas) exiting the expansion device undergoes a revers absorb or adsorb a fluid, respectively.
US 2015/0020993 A1 Jan. 22, 2015
0101. As used herein, “round trip efficiency” or “RTE' is 0109. In this embodiment, the system undergoes discharg
calculated as the power produced during expansion divided ing when desorbed working fluid is channeled from the work
by the power required for compression. ing fluid tank, along flow pathways 6 and 7, to one or more
0102. As used herein, “activated carbon is a form of heat exchangers that transfer heat to the working fluid. From
carbon processed to be riddled with small, low-volume pores the one or more heat exchangers, the heated working fluid is
that increase the Surface area available for adsorption or channeled, along flow pathway 8, to the expander wherein the
chemical reactions. working fluid undergoes Volumetric expansion. Energy is
0103) As used herein, the term “metal organic framework” discharged from system from the expander that may be
refers to crystalline compounds consisting of metal ions or coupled with a generator for producing electrical energy. The
clusters coordinated to organic molecules to form one-, two-, expanded working fluid, i.e., working fluid in a gaseous
or three-dimensional structures. In some cases, the structures physical state, is channeled, along flow pathways 9 and 10, to
are porous and the pores are stable during elimination of the the absorbent tank, wherein the working fluid is mixed or
guest molecules (often solvents) and can be used for the dissolved in the absorbent. In some embodiments, heat flows,
storage of gases. along flow pathway 11, from one or more heat exchangers to
0104. As used herein, the term “food oil” refers to oils the condensed working fluid before the fluid is expanded.
commonly used in cooking and food preparation including After the working fluid is expanded, the one or more heat
olive oil, palm oil, soybean oil, canola oil (rapeseed oil), exchangers can transfer heat, along flow pathway 12, away
pumpkin seed oil, corn oil, Sunflower oil, Safflower oil, peanut from absorbent tank where heat is generated during the dis
oil, grape seed oil, Sesame oil, argan oil, rice bran oil and other solution of the working fluid in the absorbent.
Vegetable oils. 0110. Alternatively, the system of the present invention
0105. As used herein, the term “silicone oil” refers to any may undergo discharging when desorbed working fluid hav
liquid polymerized siloxane with organic side chains. ing a liquid physical state is channeled, along flow pathway
Examples of silicone include are hexamethyldisiloxane and 13, to an expander wherein the liquid working fluid is trans
simethicone. formed into an expanded vapor. The expanded vapor is chan
0106. As used herein, the terms “first and/or “second do neled, along flow pathways 14 and 15, to one or more heat
not refer to order or denote relative positions in space or time, exchangers that transfer heat to or from the expanded vapor.
but these terms are used to distinguish between two different The working fluid is then channeled, along flow pathway 16,
elements or components. For example, a first component does to the working fluid tank, where it is stored until the system
not necessarily proceed a second component in time or space: undergoes charging or recharging.
however, the first component is not the second component and 0111. The system may undergo charging when desorbed
Vice versa. Although it is possible for a first component to working fluid is channeled, along flow pathways 17 and 18,
precede a second component in space or time, it is equally from the working fluid tank to one or more heat exchangers
possible that a second component precedes a first component and, along flow pathway 19, to the compressor, wherein the
in space or time. working fluid is compressed. From the compressor, com
II. SYSTEMS
pressed working fluid is channeled to one or more heat
exchangers, along flow pathways 20-22, to the absorbent tank
0107 Referring to FIGS. 1-4, one embodiment of the wherein the working fluid is mixed or dissolved in the absor
present invention provides a system for storing energy com bent.
prising an absorbent tank or reservoir D, wherein the absor 0112 Another aspect of the present invention relates to an
bent tank Stores an absorbent capable of dissolving a working energy storage system comprising: a working fluid reservoir
fluid; a compressor B that compresses a working fluid; a heat containing compressed working fluid; an expander that flu
exchanger A (e.g., an ambient air vaporization heat idly communicates with the working fluid reservoir and is
exchanger) that transfers heat to or from the compressed configured to expand the working fluid; an absorbent storage
working fluid; a working fluid tank or reservoir G that reservoir containing an absorbent, wherein the absorbent res
receives and stores the compressed cooled working fluid, and ervoir fluidly communicates with the expander and is config
an expander H through which the compressed working fluid ured to receive and absorb the expanded working fluid; a first
undergoes Volumetric expansion. Some examples optionally heat exchanger that thermally communicates with the absor
comprise additional heat exchangers C, E, F, I, and J that can bent reservoir and is configured to transfer heat generated by
cool or heat a working fluid or mixture of a working fluid and the absorption of the working fluid by the absorbent to the
absorbent. working fluid during the discharge of the system; a pressure
0108. In this embodiment, the system undergoes charging release mechanism configured to reduce pressure in the
or recharging when desorbed working fluid (e.g., working absorbent reservoir, a compressor that fluidly communicates
fluid in a liquid physical state) is channeled from the absor with the absorbent reservoir and fluidly communicates with
bent tank or reservoir to the compressor (e.g., a piston cylin the working fluid reservoir and is configured to compress the
der) along flow pathway 1 where the working fluid is com working fluid that desorbs from the absorbent; and a second
pressed. From the compressor, the compressed working fluid heat exchanger in thermal communication with the working
is channeled along flow pathway 2 to a heat exchanger that fluid in the compressor, in thermal communication with the
cools and/or condenses the compressed working fluid. The absorbent and working fluid in the absorbent storage tank,
cooled and/or condensed working fluid is channeled along and configured to transfer heat that is generated by the com
flow pathway 3 to the working fluid tank where it is stored pression of the working fluid, to the absorbent and working
until the system discharges energy. During the charging pro fluid in the absorbent storage tank.
cess, heat may be transferred in a closed loop, along flow 0113. In some embodiments, the working fluid comprises
pathways 4 and 5, from the compressor to the absorbent tank carbon dioxide, freon, methane, ammonia, nitrous oxide, air,
to enhance the efficiency of the system. Or Water.
US 2015/0020993 A1 Jan. 22, 2015
0114. In some embodiments, the working fluid comprises I0133. In some embodiments, the system further comprises
carbon dioxide. a separator that fluidly communicates with the absorbent
0115. In some embodiments, the absorbent comprises an storage tank and the compressor. In some embodiments the
organic amine, inorganic base, activated carbon, silica gel. separator is a centrifugal or cyclonic separator. In other
Zeolite, or metal organic framework. embodiments the separator is a demister or a filter.
0116. In some embodiments, the absorbent comprises an I0134. Another embodiment of the present invention, illus
organic amine selected from monoethanolamine, piperazine, trated in FIGS.5A and 5B, uses a liquid-density working fluid
ammonia, morpholine, diethanolamine, diglycolamine, to store energy. FIG. 5A illustrates a system according to one
diisopropanolamine, triethanolamine, dibutylamine, methyl embodiment of the present invention being discharged 200.
diethanolamine, or diethylenetriamine. For example, the The working fluid is stored in either a liquid or pressurized
absorbent comprises monoethanolamine (MEA). In some fluid state within the working fluid storage tank 202 until it is
embodiments the absorbent comprises a mixture of MEA and needed. Power is generated by allowing the working fluid to
Water. release from the working fluid storage tank 202 along flow
0117. In some embodiments, the working fluid comprises path 210 and run through a heat exchanger 208, and then
ammonia. through flow path 212 into an expander 206 (e.g., a turbo
0118. In some embodiments, the absorbent comprises a expander or piston expander) to produce work. After under
metal halide salt (e.g. MgCl2 or CaCl), mild acid, water, going expansion, the working fluid is a low density vapor.
activated carbon, silica gel, Zeolite, or metal organic frame This material is then channeled along flow path 214 to the
work. absorber storage tank 204 and condensed using either a liquid
0119. In some embodiments, the working fluid comprises or solid absorbent (or “sorbent'). In some embodiments, the
nitrous oxide. absorbent-working fluid combination has a high heat of solu
0120 In some embodiments, the absorbent comprises a tion. The heat generated from mixing the two materials is
food oil, silicone oil, activated carbon, silica gel, Zeolite, or transferred via heat exchanger 208 to heat the working fluid
metal organic framework. being delivered to the expander. At the end of a complete
0121. In some embodiments, the compressor and discharge, the working fluid storage tank will contain pres
expander comprise a reversible turbine. surized vapor, and the absorber tank will contain the absor
0122. In some embodiments, the compressor comprises a bent saturated with working fluid.
turbine, piston, radial reaction turbine. 0.135 FIG. 5B illustrates this system being charged or
(0123. In some embodiments, the expander comprises a recharged 300. Recharging the system involves separating the
turbine, piston, or turbo-expander. working fluid from the sorbent and then channeling the work
0.124. In some embodiments, the system further comprises ing fluid along flow path 310 to the compressor 306 that
an electrical generator connected to the expander. compresses the working fluid and returns the working fluid to
0.125. In some embodiments, the system further comprises the working fluid storage tank 302 along flow paths 312 and
a motor connected to the compressor. 314. In several instances, the working fluid is separated from
0126. In some embodiments, the system further comprises the absorbent either by decreasing the system pressure or
an external heat Source, in thermal communication with the increasing the system temperature, although other Suitable
expanded working fluid. methods of separation exist. During desorption, the working
0127. In some embodiments, the system further comprises fluid undergoes cooling. The cooled working fluid may be
a controller connected to the compressor (motor), expander used to condense the compressed vapor before returning the
(generator), pressure release mechanism, absorbent storage working fluid to its storage tank 302. In some embodiments,
tank, working fluid storage tank, or any combination thereof. additional heat exchangers may be used to enhance heat
0128. In some embodiments, the first heat exchanger and removal, i.e., cooling. Tanks 302,304 and heat exchanger 308
second heat exchanger each comprise high Surface area fin may be used in both discharge and recharge mode; and, only
shaped structures within the absorbent storage tank. the compressor 306 and turbo-expander 206 are unique to
0129. In some embodiments, the system further comprises each step. In some embodiments, a reversible turbine may be
one or more additional compressors, fluidly connected to and used that can be configured to function as either a compressor
positioned between the first compressor and the working fluid or expander as needed.
storage tank. 0.136 FIGS. 6A and 6B illustrate another embodiment of
0130. In some embodiments, the system further comprises the present invention. The embodiment depicted in FIGS. 6A
one or more additional expanders, fluidly connected to and and 6B show the system of the present invention operating as
positioned between the first expander and the absorbent stor an electrical energy storage system.
age tank. 0.137 In FIG. 6A, the electrical energy storage system 10
0131. In some embodiments, the pressure release mecha is discharging energy (e.g., electrical energy). This system
nism is a valve. has a power side 12 and an energy side 14. The energy storage
0.132. In some embodiments, the system further comprises and power generation may be designed to give a wide range of
a pump that fluidly communicates with the absorbent storage combinations of energy and power for many applications.
tank and a sprayer in fluid communication with the pump and The working fluid or gas exits working fluid tank 34 along
the absorbent storage tank. For example, the pump pumps the flow path 46. As the working fluid or gas exits the working
absorbent and absorbed working fluid to the sprayer and the fluid tank, it passes through one or more heat exchangers 30,
sprayer sprays the fluid back into the absorbent storage tank. 32. The heat exchangers capture the heat of reaction between
In some embodiments, the sprayer atomizes the fluid to Small the working fluid (e.g., CO) and the absorbent (e.g., an amine
droplets. In some embodiments the sprayer sprays the absor absorbent). The reaction occurs on the outer surface of the
bent over the heat exchanger with high Surface area fin heat exchanger 30 and the heat from this reaction is trans
shaped structures within the absorbent storage tank. ferred to the working fluid (e.g., CO) in the pipe of the heat
US 2015/0020993 A1 Jan. 22, 2015
exchanger. The heated working fluid (e.g., CO) is trans in the working fluid storage tank. In some embodiments, an
ported along flow path 40 to the expander 22 where the exothermic chemical reaction occurs between this liquid and
compressed or pressurized working fluid (e.g., CO) expands the incoming working fluid (e.g., CO), and heat is generated
to generate energy. In some embodiments, the expander is directly on fins of the heat exchanger 30 within the absorbent
connected to a gearbox 18 and a generator 16 through any reservoir.
Suitable mechanical connection to generate the desired elec 0143. The working fluid travels along flow paths 44, 130,
trical output. The expander (e.g., turbine) may be connected and 138 to a compressor. Electrical energy runs motor 106
to a generator of any type (e.g., AC, DC, 3-phase, or the like) that compresses or increases the pressure of the working fluid.
or the shaft power may be used for any desired purpose. The motor may operate compressor 108 or the motor may
Optionally, an additional heat exchanger 26 may provide reverse the operation of turbo-expander so that the turbo
additional heat (e.g., Sourced from waste heat or other heat expander functions to compress the working fluid. Any Suit
Source) to the working fluid prior to expansion. After expan able compressor can be used to complete this step. The pres
Sion, the working fluid may flow through an optional separa surized work fluid is channeled along flow path 128, 134, and
tor 24, and then into the absorber tank 28. 136 to the working fluid storage tank, where it is stored until
0.138. There are several suitable expansion type devices a discharge cycle begins.
available to recover the energy from expanding gases. These 0144. As illustrated in FIGS. 8A and 8B, the compressor
can be of any design and include both turbines and piston type and expander (e.g., turbo-expander) may be different devices,
motors. In general, the turbines, when used in this applica or the turbo-expander may also act as the compressor. In this
tion, are commonly called “turbo-expanders'. In some embodiment, absorbent pump 890 pumps absorbent to distri
embodiments, the expander or turbo-expander obtains con bution manifold 870 wherein the absorbent is sprayed from
version efficiency in excess of about 80% of the energy in the spray nozzles 881-884 onto the heat exchanger900 that com
expanding gas. In other embodiments, the turbo-expander prises spirally wound pipe that channels working fluid to the
obtains about 90% efficiency. In some embodiments, the expander and/or from the compressor. As illustrated, systems
expander is a radial reaction turbine (RRT). And, in some of the present invention may optionally include one or more
embodiments, the RRT is configured to run with supercritical pall rings 851-854 inside the absorbent tank and/or inside the
working fluids. Such as CO, to achieve high efficiencies. To working fluid tank. Moreover, the charging and discharging
use an RRT, the absorbent(s) are selected that match the of systems of the present invention may also be accomplished
pressure range of the output of the RRT in the system. using a controller such as valve 860, which operates to control
0.139. The critical temperature of CO, is 31° C. At this the flow path for the working fluid during charging and dis
temperature, the pressure of the CO is 56 bar. In some charging.
instances, the pressures in the RRT vary between about 50 bar 0145 Depending on how much pressure change is desired
and about 120 bar. If a solid absorbent is paired with a super in the cycle, the compressor may be one or more (e.g., 1, 2, 3,
critical working fluid (e.g., CO), the heat transfer associated 4, or more) stages. The choice of pressure range is governed
with the solid absorbent will be improved because supercriti by design choices based on absorbent properties and the
cal fluids are efficient heat transfer agents. desired energy density. Energy density is related to the oper
0140. As illustrated in FIG. 6A, during the discharge, the ating pressure since, as can be seen by FIGS. 9-11 that typical
rate of discharge is regulated by the rate of the working fluid absorbents give different amounts of working fluid (e.g.,
passing through the turbo-expander. Increases in flow rate are CO) capacity depending on pressure and temperature. Thus,
associated with increases in power output. Power output may if an absorbent that can absorb (and release during recharge)
be controlled by standard control valves or mass flow con more working fluid (e.g., CO.) than another absorbent will
trollers. A higher flow rate also means that more working fluid have a better energy density compared with the other absor
(e.g., CO) is entering the absorbent reservoir and more heat bent that does not absorb as much working fluid (e.g., CO)
is generated from the reaction of the working fluid with the per unit volume of absorbent.
absorbent. This heat corresponds with the increased amount 0146. As shown in FIG. 12, heat flux is given in units of
of working fluid that requires heating at these higher rates. area and time. Thus, greater Surface area of heat exchanger
Thus, heat is generated in Suitable amounts as needed, and fins leads to higher reaction rates and allows for faster work
there is no requirement to store a hot gas or liquid for use at a ing fluid (e.g., CO) absorption and higher power generation.
later time. Moreover, this heat does not need to be transported or stored.
0141. In systems of the present invention, heat exchangers It is available to go directly back to the working fluid that is
can possess any suitable configuration. FIGS. 7A and 7B about to be expanded in the expander (e.g., turbo-expander or
illustrate one configuration for optional heat exchanger 26 in piston). Alternatively, excess heat could be transferred to a
accordance with the present invention. In this configuration, secondary heat transfer fluid that could then be pumped to a
cold working fluid or a mixture of cold working fluid and cold site where heat is desired.
absorbent is channeled through serpentine piping 550 that 0.147. In some embodiments, the vacuum action of the
thermally communicates with heat exchanger fins 510. Cold intake side of the compressor will be sufficient to allow work
working fluid or mixture enters the serpentine piping 530 and ing fluid (e.g., CO) to be released from the absorbent. In
exits as heated working fluid or a heated mixture 540. This these embodiments, this is an endothermic reaction and the
optional heat exchanger can also be used to extract heat from absorbent will cool. However, the action of compressing the
other sources Such as waste heat in any form or even from the working fluid will generate heat. In some embodiments, this
environment if the ambient temperature is above the tempera heat is removed to maintain efficiencies. Further, the absor
ture of the fluid or gas entering the turbo-expander. bent cannot cool indefinitely, so as the absorbent cools, heat
0142 Referring to FIG. 6A, the absorbent is a pumpable generated in the compressor heats the absorbent. The heat
liquid that may be pumped along flow path 38 by pump 20, in going to the absorbent may drive the endothermic reaction
this example, directly over the heat exchanger 30 and stored and facilitate the release of additional working fluid (e.g.,
US 2015/0020993 A1 Jan. 22, 2015
CO) for compression. This continues until the working fluid one or more compressors C1-C5 returning to higher pressure
(e.g., CO) tank is full or until it is desired to stop the recharg carbon dioxide. Thus, the working fluid (e.g., CO gas) enters
ing process. into the next cycle.
0148. Accordingly, systems of the present invention may 0153. In another loop, the low concentration liquid work
be charged or discharged and reversed at any part of the cycle. ing fluid and absorbent Solution (e.g., CO and ammonia
These systems may also be run at any power level even its solution) exiting the reboiler is circulated into the chamber
maximum power right to the very end of the cycle. It may be containing HX1 and HX2 heat exchangers. Working fluid gas
discharged to 100% depth of discharge as often as desired and (e.g., CO gas) is further separated from absorbent (e.g.,
at full power as well with no detrimental effects to the system. ammonia) in this chamber and circulated via heat exchanger
0149. In some embodiments, during the recharge cycle, as Hx3 into compressors C1-C5. Thus, the working fluid (e.g.,
the working fluid (e.g., CO) is being released from the absor CO) gas enters into the next cycle.
bent, some absorbent may become entrained in the working 0154 Another embodiment of the mechanical-chemical
fluid. Should this be the case, an optional separator 24 may be energy storage system is described in the schematic diagrams
placed between the absorbent reservoir and the intake to the shown in FIGS. 15A and 15B. During discharging, high pres
expander (e.g., turbo-expander). In some embodiments. Such Sure working fluid undergoes expansion wherein the
as the embodiment illustrated in FIGS. 6A and 6B, the sepa expander (e.g., a turbine or turbo-expander) can generate
rator is a centrifugal or cyclonic separator. In other embodi electrical energy when coupled with a generator. The
ments, the separator may comprise a simple demister or filter. expanded working fluid is absorbed by the absorbent in a
reaction vessel. When the system is charged, the working
0150. Another embodiment of the mechanical-chemical fluid is separated from the absorbent and channeled to a
energy storage system is described in the schematic diagram multistage compressor wherein the working fluid is pressur
shown in FIG. 13. This closed loop system contains several ized and returned to a working fluid tank as a high pressure
loops. In this embodiment, to avoid any corrosion of com working fluid. The heat generated during the compression of
pressor blades, precautions are taken to prevent the entry of the working fluid may be transferred to the reaction vessel to
absorbent (e.g., ammonia) or working fluid-absorbent mix power the release of the working fluid via aheat exchanger, or
ture (e.g., carbon dioxide ammonia mixture) into compres the heat may be transferred to high pressure working fluid
sors. Starting with the fully charged system, high pressure before it is expanded through the expander.
carbon dioxide (labeled “high pressure CO) expands (O155 Working Fluids
through an expansion device or series of expansion devices
El-E3 to generate power. Examples of suitable expansion 0156 All suitable working fluids are within the scope of
devices include turbo-expanders. the invention. Suitable working fluids can be expanded and
compressed and can be absorbed by an absorbent. Exemplary
0151. In one loop, the expanded working fluid (e.g., CO) working fluids include fluids that can be compressed to a
or exhaust from the expansion device travels through heat liquid, critical, or trans-critical state at the desired operating
exchanger (HX3). Later, this low-pressure working fluid (e.g., pressures and temperatures. For example, the desired tem
CO gas) labeled “low pressure CO is compressed by one or perature may be ambient temperature (about 20 to 25°C.) and
more compressors C1-C5 returning to higher pressure carbon the desired pressure range may be from about 40 to 60 bar,
dioxide phase. During the compression of the carbon dioxide thus, exemplary working fluids would be in a liquid, critical,
gas, which is an exothermic process, heat is captured by one or trans-critical state at those conditions. Some exemplary
or more heat exchangers H4-H 7. working fluids will be absorbed by the absorbent in a revers
0152. In another loop, the expanded working fluid or ible and/or exothermic process. Some specific exemplary
exhaust from the expansion device reacts with an absorber working fluids include carbon dioxide (CO), ammonia
(e.g., aqueous ammonia (~36% solution)) in an exothermic (NH), nitrous oxide (NO), air, and water.
reaction that generatesheat while absorbing the working fluid O157 Examples of suitable working fluids are described in
(e.g., CO). Thus, this additional energy increases the Table 1.
enthalpy of the working fluid allowing for a greater energy
production from this part of the cycle. Since the temperature TABLE 1
of the absorbent is higher than the temperature of the cooling
working fluid, energy will naturally flow in the desired direc Working fluids.
tion shown by the arrow in the discharge portion of FIG. 13. Latent Melting
Higher pressures and lower temperature of operation benefit Heat of Point
reductions of absorbent (e.g., ammonia) concentration in the Working Fluid Additive Fusion (J/g) (° C.)
working fluid (e.g., CO) phase. This heat energy powers the Fatty Acids
transfer of the organic amine (e.g., aqueous ammonia) and
working fluid (e.g., CO) Solution to a reboiler kept to a Hexadecane Na Mont- 126
temperature of about 180° F., wherein the solution separates morillonite
into the working fluid (e.g., CO gas) and the organic amine Fatty acids Surfactants 191
Oleic acid CuO
(e.g., aqueous ammonia). The partial amount of wet working Myristic acid palmitic acid 190 61
fluid (e.g., CO) and absorbent (e.g., ammonia gas) is pumped Capric acid 170 36
into the heat exchanger chamber containing HX 1-HX2. Dur Capric acid Nanotubes 75 36
ing this process further separation of working fluid (e.g., Lauric acid
Myristic acid
188
2O1
49
61
CO) and absorbent (e.g., ammonia) occurs and the gas pass Palmitic acid 185-220 67
ing through the heat exchanger HX3 is essentially pure work Stearic acid 220 73
ing fluid (e.g., CO). Later, this low-pressure working fluid Dodecanoic acid 190 42
(e.g., CO gas) labeled “low pressure CO is compressed by
US 2015/0020993 A1 Jan. 22, 2015
TABLE 1-continued TABLE 1-continued

Working fluids. Working fluids.
Latent Melting Latent Melting
Heat of Point Heat of Point
Working Fluid Additive Fusion (J/g) (° C.) Working Fluid Additive Fusion (J/g) (° C.)
Lauric acid stearic 131 33 Dissolved Gases'
acid
Stearic acid Bentonite 84 73 SO 331 62
Paraffins CO
NH
Paraffin 173 64 NO
Paraffin waxes Nanotubes 60 halons
Paraffin Graphite 18O 40 alcohol vapor
Paraffin SiO2 110 gaseous hydrocarbons
Paraffin Fe2O3 47 freons
Paraffin Siloxane 160 35 Molten Salts
Nonacosane 240 64
Hexacosane 257 56 Na2SO4*10H2O 32.4
Organics Solid PCM
Tetrabutylammonium 2OO Pentaglycerin 192 81

clathrates 2-amino-2-methyl- 264 78
Tetradecanol Graphite 220 36 1,3-propanediol
Naphthalene 148 8O Misc. Materials
Erytritol 340 118
Camphene 238 50 oleochemical 144-227 from -6 to 47
1,3-ditetradecanoyl 126 48 carbonates
thiourea
Salt Hydrates 'Possible solvents for freons, hydrocarbons and Nitrous oxide include butanediammine,
2-diethylamino ethanol, aqueous Naglycinate solution, diethanolamine, olive oil, aqueous
Glauber's salt polyacrylomide 270
hydroxide solution, dodecane, ammonia water, amine based solvent (e.g., Stonvent), veg
32 etable oil, paraffins, or any combination thereof,
(Na2SO, * 10H2O)
Glauber's salt Gelatin 248 0158. Absorbents
(Na2SO, * 10H2O)
Hydrate salts 103
0159 All suitable absorbents are within the scope of the
CaCl2, MgCl2 + SrCl
21 invention. Suitable absorbents agents are capable of chemi
NaCO*10H2O 247 33-36
cally absorbing a working fluid. Exemplary absorbents will
- 0
NaHPO 87HO 135-170 48 absorb the working fluid in a reversible and/or endothermic
MgSO,7HO 2O2 49 process. Some specific exemplary absorbents include: absor
Ba(OH)*8HO 26S-28O 78 bents of carbon dioxide, Such as organic amines (e.g., mono
CHCOONa3HO 270-290 58 ethanolamine (MEA), piperazine, ammonia, morpholine,
CHCOONa3HO Graphite
NaOH HO 272 ss diethanolamine, diglycolamine, diisopropanolamine, trietha
Eutectic Mixtures nolamine, dibutylamine, methyl-diethanolamine, or diethyl
enetriamine), inorganic bases (e.g., potassium carbonate,
Naphthalene + Benzoic 123
67 ammonium carbonate), activated carbon, silica gel, Zeolites,
acid
AlCls + NaCl + ZrCl2 234 and metal organic frameworks; absorbents of ammonia, Such
Long Chain Polymers 68 as salts that form ammonates, halide Salts (e.g., magnesium
PEO carbon black 120-170
chloride (MgCl), calcium chloride (CaCl)), mild acids,
PEO Graphite 130-160
60 water, activated carbon, silica gel. Zeolites, and metal organic
PEO carbon fibers 140-18O g frameworks; absorbents of nitrous oxide. Such as oils that
PEO Fullerenes 160-18O 60 dissolve nitrous oxide (e.g., food oils, silicone oils), activated
PEO SWCNT 1SO-18O 60 carbon, silica gel, Zeolites, and metal organic frameworks:
PEO Cellulose 40-130 60 and absorbents of air Such as activated carbon and Zeolites.
PEO Starch 47-97
PEG Chitosan 140
60 The terms “absorption agent”, “absorbent, and “sorbent are
PEG Cellulose 60 . used interchangeably and may each refer to either a liquid or
PEG 35,000 167 68 a solid agent that can absorb or adsorb a fluid, respectively.
PEG 35,000 lauric acid 186 0160 Examples of pairs of absorbents and working fluids
PEG 3400 lauric acid 188 suitable for use in the present invention are described in Table
2.
TABLE 2
Working fluids and absorbents.
Working Hads:
Fluid Absorbent (kJ/mole) Pressure
CO CO silicas --5-15
CO, organic and inorganic --1-40
carbonates
CO absorbent carbons --5-15
US 2015/0020993 A1 Jan. 22, 2015
10
TABLE 2-continued
Working Hads:
CO clays --5-5
CO aluminas --5-15
CO zeolites --5-15
CO, amine and methyl <5 -1 bar
Substituted MOF
CO various coals -12-13 up to 200 bar
CO MOF -16-20
CO, carborane based MOF -22 up to 10 bars
CO DABCO based MOF --20-24 up to 25 bars
CO MOF ~22-24
CO Au in range of
22-26
CO Zeolitic imidazolate ~21-30
CO modified MOF -26
CO MOF BTC framework 27-37
CO, carbon sorbent 28-25.7 -1 bar
CO Cr-phthalate -30 up to 30 bar
CO Zeolite 13X -31 -2 bar
CO MOF ~33, -22 up to ~5 bar
CO, chabazite -35
CO fluoro-functionalized ~45
metal oxide framework decreasing
to -30
CO metal oxide framework ranges from 1-50 bar
16-41
CO silica foam 43 up to 1 bar
CO, unsaturated metal 22, 32, 45,
centers 47-52,
44-54
CO zeolite 13X and 46 and 41 1 bar
Mg2(dobdc) respectively
CO molecular porous ~47
material
CO benzene-dicarboxylate 30-50
CO, methyl diethanolamine --SO-58
(aq)
CO ionic liquids 8O 2-3 bar
CO chabazite zeolites up to ~10 bar
CO, hydromagnesite
CO imidazolium based ionic up to ~20 bar
liquids
CO MOF 0-5 bar
CO, Zn(II)-cyclen
CO silicon nitride
CO TBAB (aq)
CO Triethylbutylammonium
Acetate
CO porous organic
polymers
CO clathrate hydrates
CO aminosilicates
CO Hydrated salts
CO MOF 177 up to 20 bar
CO, Triethylbutyl
ammonium acetate
CHA CH various carbons ~10-11
CH various coals ~10-11
CH MOF -11-12
CH zeolites -14 90 bar
decreasing
to -6
CH carborane based MOF -15 20 bar
CH Zeolite 13X 15 -2 bar
CH DABCO based MOF -14 to -18 25 bar
CH Zeolite templated carbon 16-20
CH MOF ~21, -18 up to ~5 bar
NH NH salt ammonates S-45
(CaCl* 6NH)
NH, thiocyanate
NH ammonia borane 1-4 bars
NH CaCl2 - vermiculite ~40 up to 4 bar
US 2015/0020993 A1 Jan. 22, 2015
11
TABLE 2-continued
Working Hads:
NH SrCl2 -amine -33 -2 bar
NH MgCl2 55-87 5 bar
NO, NO, biochar 20-27 for -1 bar
biochar,
-10 for
Al2O3,
Fe2O3 and
peat
CO CO DABCO based MOF -10 to -12 25 bar
CO MOF ~45, -23 up to ~5 bar
CO Nior Fe powder
CO CO complexes
Ar, N2, O2 Ar, N2, O2 carbon Sorbent 16-17 -1 bar
H2 H2 zeolite 3.5 and
higher
Ne Ne chabazite --5
Air Air chabazite -15
Air various coals -14-16
ethylene + ethylene + NaX zeolite 28-40
ethane ethane
N N various coals -8
freons, reons, various carbons -8
halons 8IOS
reons, various silicas -8
8IOS
reons, various Zeolites -8
8IOS
reons, various clays -8
8IOS
reons, various MOFs -8
8IOS
reons, various aluminas -8
8IOS
reons, graphene -8
8IOS
reons, graphite oxide -8
8IOS
8IOS
8IOS
NO NO NO complexes -10-20
HO HO salt hydrates S to 45
HO silicas S to 45
HO zeolites S to 45
HO aluminas S to 45
HO various MOFscarbons S to 45
HO inorganic and organic S to 45
oxide-hydroxides both
III. MECHANICAL CHEMICAL ENERGY 0164. In some implementations, the absorbent comprises
STORAGE METHODS an organic amine, an inorganic base, an activated carbon,
silica gel, a Zeolite, a metal organic framework, or any com
0161. One aspect of the invention relates to a method for bination thereof.
storing energy comprising: providing an absorbent reservoir 0.165. In some implementations, the absorbent comprises
containing a working fluid that is chemically absorbed by an an organic amine selected from monoethanolamine, pipera
absorbent; desorbing the working fluid from the absorbent in Zine, ammonia, morpholine, diethanolamine, diglycolamine,
an endothermic process; and condensing the working fluid in diisopropanolamine, triethanolamine, dibutylamine, methyl
an exothermic process and transferring the condensed work diethanolamine, diethylenetriamine, or any combination
ing fluid to a working fluid reservoir under pressure; wherein thereof. For example, the absorbent comprises monoethano
at least Some of the heat generated during the condensing step lamine (MEA). In some implementations the absorbent com
is recycled to drive the desorbing step. prises a mixture of MEA and water.
0162. In some implementations, the working fluid com 0166 In some implementations, the working fluid com
prises ammonia.
prises carbon dioxide, ammonia, nitrous oxide, air, or water. 0167. In some implementations, the absorbent comprises
0163. In some implementations, the working fluid com a metal halide salt, a mild acid, water, activated carbon, silica
prises carbon dioxide or ammonia. gel, a Zeolite, or metal organic framework.
US 2015/0020993 A1 Jan. 22, 2015
0.168. In some implementations, the working fluid com 0185. In some implementations, the working fluid com
prises nitrous oxide. prises nitrous oxide.
0169. In some implementations, the absorbent comprises 0186. In some implementations, the absorbent comprises
a food oil, silicone oil, activated carbon, silica gel, Zeolite, or a food oil, silicone oil, activated carbon, silica gel, Zeolite, or
metal organic framework. metal organic framework.
0170 In some implementations, the heat generated from 0187. In some implementations, the heat generated during
the condensing step is recycled to drive the desorbing step the condensing step is recycled drive the desorbing step using
using a heat exchanger. a heat exchanger.
0171 In some implementations, the method further com 0188 In some implementations, the working fluid is com
prises compressing the working fluid using a reversible tur pressed by a reversible turbine.
bine.
0172. In some implementations, the method further com 0189 In some implementations, the method further com
prises compressing the working fluid and storing the working prises compressing the working fluid and storing the working
fluid in the working fluid reservoir in a liquid state, a critical fluid in the working fluid reservoir in a liquid state, a critical
state, or a trans-critical state. state, or a trans-critical state.
0173. In some implementations, the working fluid is com 0190. In some implementations, the working fluid is com
pressed to and stored at a pressure of from about 1 bar to about pressed to and stored at a pressure of from about 1 bar to about
200 bar (e.g. 10 bar to 100 bar, or about 50 bar). 100 bar, (e.g. from about 10 bar to about 100 bar, from about
0.174. In some implementations, the method further com 20 bar to about 80 bar, or about 50 bar).
prises a second compression stage after the first compression. 0191 In some implementations, the compressing step
0.175. In some implementations, the working fluid is comprises a two-stage compression process.
expanded to a pressure of from about 0.1 bar to 10 bar (e.g., 0.192 In some implementations, the working fluid is
about 0.5 bar to about 5 bar, or about 1 bar). expanded to a pressure of from about 0.1 bar to 10 bar (e.g.
0176). In some implementations, the working fluid is about 1 bar).
stored at ambient temperature. 0193 In some implementations, the working fluid is
0177. In some implementations, the method further com stored at ambient temperature.
prises heating the working fluid prior to expansion using an 0194 In some implementations, the method further com
outside heat source. prises heating the working fluid prior to expansion using an
0.178 Another aspect of the invention relates to a method external heat source.
of charging and discharging an energy storage system com (0195 In some implementations, the method further com
prising: (1) charging the system comprising: providing an prises directing the flow of the working fluid a first direction
absorbent storage tank containing a working fluid that is during charging, and reversing the flow of the direction of the
chemically absorbed by an absorbent; desorbing the working working fluid during discharging.
fluid from the absorbent in an endothermic process; condens 0196. Another aspect of the mechanical-chemical energy
ing the working fluid in an exothermic process and transfer storage systems of the present invention are illustrated in
ring the condensed working fluid to a working fluid reservoir FIGS. 14A-14C. Starting with a fully charged system, as
under pressure; and recycling heat generated during the con shown in FIG. 14C, the system uses CO as a working fluid,
densing step to drive the desorbing step; and storing the but it is not limited to this working fluid. There is a full tank
working fluid in a working fluid reservoir under pressure; and of a liquefied or supercritical CO labeled “liquefied gas” that
(2) discharging the system comprising: expanding the work is expanded through an expansion device such as a turbo
ing fluid; chemically absorbing the working fluid with the expander to generate power. As the working fluid expands, its
absorbent in the absorbent reservoir in an exothermic process; enthalpy reduces and it cools. The exhaust form the expansion
recycling heat generated during the absorption reaction to device is now reacted with an absorber, Such as an organic
drive the expanding step; and storing the absorbent and the amine, such as MEA, that generates heat while absorbing the
absorbed working fluid in the absorbent reservoir. CO. This heat is beneficially used by transfer to the cooling
0179. In some implementations, the working fluid com CO gas on the input side of the turbo-expander. Thus, this
prises carbon dioxide, ammonia, nitrous oxide, air, or water. additional energy increases the enthalpy of the working fluid
0180. In some implementations, the working fluid com allowing for a greater energy production from this part of the
prises carbon dioxide. cycle. Since the temperature of the absorbent medium is
0181. In some implementations, the absorbent comprises higher than the temperature of the cooling working fluid,
an organic amine, inorganic base, activated carbon, silica gel. energy will naturally flow in the desired direction shown by
Zeolite, or metal organic framework. the arrow in the discharge portion of FIG. 14C. This process
0182. In some implementations, the absorbent comprises may continue at any desired rate or rates until all of the CO
an organic amine selected from monoethanolamine, pipera or other working fluid has been removed from the tank. It is
Zine, ammonia, morpholine, diethanolamine, diglycolamine, however, not necessary to completely discharge the tank, if it
diisopropanolamine, triethanolamine, dibutylamine, methyl is desired to start a recharge cycle. It may be reversed at any
diethanolamine, or diethylenetriamine. For example, the time that is desired.
absorbent comprises monoethanolamine (MEA). In some 0.197 When it is desired to recharge the system, the
implementations the absorbent comprises a mixture of MEA reverse process is shown in the charge portion of FIG. 14B.
and water. Here, energy is input to reverse the chemical reaction and
0183 In some implementations, the working fluid com release the working fluid as a gas, which lowers the enthalpy
of the absorbent. The working fluid gas is then compressed to
prises ammonia. the pressure required to create a liquid or Supercritical fluid.
0184. In some implementations, the absorbent comprises During this compression, heat is generated. Recovering this
a metal halide Salt (e.g., MgCl, CaCl2), mild acid, water, heat via the use of a heat exchanger raises the RTE of the
activated carbon, silica gel, Zeolite, or metal organic frame system. This heat is transferred to the absorbent(s). This heat
work. continues to drive the release of the working fluid from the
US 2015/0020993 A1 Jan. 22, 2015
absorbent. This process may be continued at any desired rate 0204. These are also all exothermic reactions. Thus, the
or rates until the working fluid (e.g., CO) tank is full. In this heat that is released can be used to expand the ammonia to get
embodiment, it is not necessary to completely recharge the addition energy from the system. Note that this heatenergy is
tank. If it is desired to starta discharge cycle before the filling generated when and as the system discharges. It is not stored
of the working fluid tank, the cycle may be reversed before the as heat but used rightaway to create more energy and increase
working fluid tank is full. the efficiency of the system.
0198 Another aspect of the present invention provides a 0205 Further, removing ammonia during the recharge
method of storing energy using mechanical-chemical energy step will drive the reactions to the left and create a source of
storage system is described in FIG. 16. This implementation cold to help with the liquefaction of ammonia. Again this cold
comprises charging the system by compressing a working is not stored as a cold material but is generated as the recharg
fluid (e.g., CO) in a series of compressors C10-C40, i.e., ing process takes place.
multi-stage compression, and storing the compressed work 0206. In this case, the vacuum at the intake of the com
ing fluid in a working fluid tank. Charging, according to this pression device could be sufficient to start removing ammo
implementation, also comprises removing or transferring the nia from the MgCl*NH and drive the recharge reaction. The
heat generated during the multi-stage compression from the additional heat from the compression of the ammonia can
working fluid using heat exchangers HX40-Hx70 that are also drive the release of the ammonia until the recharging is
arranged between compressors or operated between Succes complete.
sive compression stages.
0199 Some implementations further include discharging Example 2
energy from the mechanical-chemical energy storage system.
Discharging energy from this system comprises expanding Carbon Dioxide and Monoethanolamine
the working fluid through expanders (e.g., turbines, turbo
expanders, pistons, or any combination thereof) E10-E30. 0207 Monoethanolamine (MEA), usually as a 30% solu
One or more heat exchangers Hx80, HX 10, and HX20 transfer tion in water, has been used for many years for removal of
heat to the working fluid. The one or more heat exchangers are CO from natural gas.
arranged to input heat to the working fluid between Succes 0208. The simplified chemical equations representing
sive expansions. In some instances, the heat exchangers are these reactions include:
arranged along the working fluid flow path between expand
ers. Alternatively, a single heat exchanger can inputheat to the
working fluid between Successive expansions. MEA+HCO==>MEAHCO+HO (8)
IV. EXAMPLES
0209. These reactions are exothermic and give off heat as
CO is absorbed. These are essentially simple acid-base reac
Example 1 tions that are easily reversible since they are not too exother
1C.
0210. The fact that a gas is part of the equilibrium helps the
Ammonia and Magnesium Chloride reaction be driven in either direction by change of gas pres
0200 Magnesium chloride can form ammonates. MgCl2 Sure. This allows for the storage of energy as chemical poten
can absorb up to 6 molecules of ammonia to form tial and allows for the control of this reaction by pressure and
MgCl, *6NH. temperature.
0201 The pressure of the ammonia over the MgCl, varies 0211 Thus, as CO exits the turbo-expander, the equilib
as more or less ammonia is incorporated into the molecular rium in reaction 7 is pushed to the right, which also pushes
structure. Since the salt and its ammonate are solid, the heat reaction 8 to the right, releasing heat energy as needed to
generated from the reaction needs to be allowed to move to expand the CO, further.
the cooling ammonia by either packing the salt on one side of 0212 FIGS. 7A and 7B shows one possible configuration
aheat exchanger and having the ammonia on the other side of of a heat exchanger for transferring heat. In the embodiment
the same heat exchanger or by having an intermediate heat of FIGS. 7A and 7B, MEA (absorbent) is allowed to fall over
transfer fluid carry the heat away from the salt and deliver it to the outer fins of a heat exchanger. While the CO gas (working
the ammonia. fluid) is allowed to react with the MEA in the same area. The
0202 Simplified chemical equations representing these high Surface area fins increase the reaction rate by exposing a
greater amount of MEA to the CO. As the MEA and CO,
react, the heat is then directly available to any fluid inside the
pipes of the heat exchanger. This can be the pressurized CO
going into the turbo-expander or it can be an intermediate heat
exchange fluid (such as water) that can be pumped where the
heat is desired.
0213 FIG. 18 is a typical graph showing the rate of CO
absorption per unit area and time. FIG. 9 is a typical loading
graph showing how much CO can be absorbed at various
pressures.
0214. These relationships, shown in FIGS. 18 and 9, can
be used to design systems with a CO working fluid. The
0203 As NH pressure is increased all of the above reac power and absorption rate can be calculated using FIG. 12 for
tions will go to completion (to the right). This is the case as the the particular absorbent and pressure temperature ranges. The
System is discharging. required amounts of CO and (in this case MEA) can be
US 2015/0020993 A1 Jan. 22, 2015
calculated by determining how many moles of CO2 are higher inlet temperatures and at larger pressure drops across
absorbed and released under the intended operating condi the expander. For the expander, it is preferred to maximize the
tions of the system. power output during the discharge step.
0215. As an example, a system may have a vacuum side of 0221 Referring to FIG. 20, a similar study was performed
the compressor that will operate at 100 pascals and will with the compressor. Similar results were obtained as to the
charge the MEA up to 100,000 pascals. The amount of CO, expander, higher temperatures lead to higher power inputs to
can then be calculated by finding those two points on the compress the CO, and a greater pressure difference across
graph where the line crosses and reading down to how much the compressor requires greater power input. Compression
CO, is absorbed by the MEA at those pressures. In this case, occurs during the recharge step, so it is preferred to minimize
when charging at 100,000 pascals, the mole ratio is about 0.6 the power input to repressurize the CO.
moles of CO, per mole of MEA. Down at the lower pressure 0222. In order to improve the performance of compressors
the ratio is about 0.2 to 1. These two ratios are subtracted and and expanders, multiple stages are often employed. For
it is determined that the capacity of the MEA operation example, in the calculations used in FIG. 20 it was assumed
between these pressures will cycle at about 0.4 moles of CO that the CO, was pressurized up to 900 psia from the starting
per mole of amine. It should be noted that these curves are at pressure; this would be a one-stage process. For the purpose
a single temperature. of the simulation, multiple expander or compressor units are
0216 FIG.10 shows that if the temperature is shifted in the modeled in series with heat exchangers to add/remove heat, as
correct direction that the capacity can also be increased. As needed. FIG. 21 shows the variation in power input required
the absorber is being charged if its temperature is lowered it to a compressor when it is run with 1-3 stages.
will absorb more CO at any given pressure. This is of course 0223 For the two-stage process, the first stage pressurized
precisely what the invention does while the system is dis the 80° F. working fluid from 200-425 psia; the compression
charging. Further, as the absorbent is heated it will release caused the fluid to warm, so a heat exchanger is used to reduce
more CO, than would otherwise be released at that same the temperature to 80° F. Then the second stage is run to
pressure. This is also precisely what happens during recharge pressurize from 425-900 psia.
when we would want more pressure at the intake side of the 0224 For the three-stage process, the first stage pressur
compressor. ized the 80° F. working fluid from 200-330 psia; the compres
0217 FIG. 10 shows the pressure of CO at 40 and 60° C. sion caused the fluid to warm, so a heat exchanger is used to
over MEA/PZ. As can be seen by the two lines in FIG. 10, at reduce the temperature to 80°F. Then the second stage is run
all points, the pressure of CO at 60°C. is greater than that of to pressurize from 330-550 psia. Again, the compression
CO, at 40°C. Thus, by cooling the MEA during absorption heated working fluid is cooled to 80° F. and then enters the
and heating during desorption and by using the chemical third stage where it achieves a final pressure of 900 psia.
potential of the MEA reaction, the efficiency of the system is 0225. As can be seen in FIG. 21, the additional stages
maximized. This graph also shows that an increase of about reduce the power input required to pressurize the CO, work
0.2 moles of CO per mole of amine can be obtained by ing fluid. The difference is more significant between moving
swinging the temperatures between 40°C. and 60° C. during from one to two stages than from going two to three stages.
the discharge and recharging, respectively. 0226. Of particular interest in evaluating the process will
0218 FIG. 11 shows an example of advanced metal be the percentage of the recharge power that can be delivered
organic frameworks (MOFs) and activated carbon. These in discharge mode; this will be referred to as the Round Trip
materials have a high capacity for storage of carbon dioxide at Efficiency (RTE). The minimum acceptable value for this
room temperature. These materials have a wide range of process is 0.6 (60%). FIG.22 shows the calculated RTE for a
pressures to choose from for design considerations and are in system operating between 200-900 psia.
some cases capable of absorbing over 100% of their own 0227. One method to improve power output is to pressur
weight in CO. ize the liquid CO with a standard pump when it leaves the
Example 3 storage tank, and then add heat to move the working fluid into
a Supercritical state. This approach works because the power
required to pressurize a liquid is significantly lower than the
Process Simulation No. 1 —(CO/MEA) power output that can begained from the expander (assuming
0219. In order to simulate an exemplary process, a a heat source is available, of course). FIG. 23 shows the
CHEMCAD simulation software package was used. The pro improvement in RTE when the working fluid is delivered to
cess was simulated in sections rather than in a single simula the expander at 1400 psia.
tion to allow for the use of different models for the fluid 0228. Up to this point, the sorbent has not been considered
properties in certain segments of the process. Initial simula in the analysis. All of the above calculations look at CO, and
tions were performed assuming a constant CO mass flow rate the power generated or consumed during discharge or
(1 lb/sec) and assuming negligible carryover of any impuri recharge steps. The choice of sorbent is important for the
ties or Sorbents through the expansion/contraction steps. It is system design. Of particular interest for the preceding analy
also assumed that the heat of solution of the CO and sorbent sis is the heat of solution. It has been assumed that the energy
is capable of heating the Solution to the fixed set point tem needed to heat the working fluid is available. One sorbent of
perature for the calculation. Therefore, it must be noted that interest is monoethanolamine (MEA). It has a high heat of
the highest temperatures in the simulations below may not be solution with CO. Using the CHEMCADAMINE model, it
achievable without additional heat input (this will be dis is possible to calculate the temperature of CO/MEA mixed
cussed further). solutions. One simulation looked at mixing 100% pure MEA
0220. Using a single stage expander, FIG. 19 shows the with CO, and it was found that ~17 wt.% CO was dissolved
variation of expander power output at varying process condi and the final solution temperature achieved 330°F. Using this
tions. As would be expected, greater power output occurs at heated sorbent as the heat supply for the CO heat exchanger
US 2015/0020993 A1 Jan. 22, 2015
prior to the expander, we found that it was possible to heat the TABLE 3-continued
CO to 280°F. in two expansion stages. The outgoing sorbent Discharge Sorption T = 160 F.
stream still retained a significant amount of heat, as the outlet
temperature was ~290°F. after heating the CO. Streams Unit Ops
0229. In order to achieve a high sorbent temperature, the T(F) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source
MEA sorbent must dissolve a significant amount of CO. 1 70 856 A. +68.5 Air
FIG. 18 shows the variation of temperature in MEA when 2 8O 856 B +28.1 System
CO is added. To achieve high temperature (over 300°F), the 3 150 856 C 54.5 -81.3 Exp. Cooling
MEA must dissolve over 14 wt % CO. That means that 4 150 1OO D +81.3 System
significant CO desorption must occur during the recharge 5 160 1OO E +2.3 System
step so the MEA will have the capacity to take up that much Recharge Desorption T = 60 F.
working fluid during the discharge step.
Unit Ops
Example 4 T(F) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source
1 70 1OO A. -61.3 Air
Process Simulation No. 2 2 70 856 B 78.2 +83.0 Comp Heat
3 70 856 C -83.0 System
0230. Another exemplary process was simulated using the
Software package described above. The following assump Hads 111.7 kJsec
RTE O.70
tions were made: 1)All streams can be heated or cooled to 80° 10.8 kJ/mol
F. from the atmosphere, whetherheating or cooling. All phase
change energy is Supplied from the atmosphere. Energy to run
the air blowers is neglected. 2) Working fluid liquid inlet 0232 To balance a system, such as the system described in
condition is set at 70°F., where the fluid is a liquid at its vapor this example or the other embodiments described herein,
pressure. 3)Pressure is set between 100-856 psia and 200-856 calculation of the minimum heat and maximum temperature
psia. 4) Piston work is calculated as PdV. A simple curve fit of of the absorber may be useful. Two criteria should be met. The
Pressure to Volume information was used for the integration. first is the minimum heat of reaction required for the absorber.
5) Piston heat is calculated as TaS. 6) Assumed inefficiencies This is calculated by dividing the amount of energy required
remained the same as with isentropic process—85% for to reverse the chemical reaction of the working fluid with the
expansion, 75% for compression. Lost energy is not absorber (the B unit op column Q in the recharge cycle
accounted for in the simulation. 7) RTE is calculated as the above) by the number of moles of working fluid needed to
power produced during piston expansion divided by the create a given amount of energy, which in this model is set at
power required by the piston compression. 1#/sec. Thus, for CO, in this case is 10.32 moles.
0233. So in the example above Q=56.2 kJ this divided by
0231. A schematic of the process used for the simulation is 10.32 moles=5.45 kJ/mole as a minimum reaction energy
shown in FIGS. 1 and 2 for recharge and discharge, respec (delta G) for each mole of working fluid that reacts with each
tively. Process conditions and the resulting RTE are shown in mole of absorber. The order of magnitude of this energy is
Table 3, below. A CO model was used to model the working actually very low compared to most chemical reactions.
fluid for the simulation. While it is good to have a delta Glarger than the minimum it
also needs to be reversible at a temperature that is available
TABLE 3 from the heat of compression. In general the higher the delta
G the higher the temperature (and or pressure differential)
Discharge Sorption T = 160 F. that will be required to reverse the reaction. There is no exact
Streams Unit Ops
formula that relates delta G to the temperature so each system
has to be considered to make sure that it is reversible. Zeolites
and activated carbons have delta G values of about 5 to about
T(F) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source
20 kJ/mole for CO and NH working fluids. Another
1 70 856 A. +68.5 Air example is water and CO2 going to HCO, which has a delta
2 8O 856 B +28.1 System G of about 12 kJ/mole. Many of these compounds can easily
3 150 856 C 35.2 -55.0 Exp. Cooling be desorbed by allowing the pressure to decrease on them.
4 150 2OO D +55.0 System
5 160 2OO E +2.4 System 0234. In the case of a solid absorbent, a secondary heat
transfer loop using an inert heat transfer liquid may also be
Recharge Desorption T = 60 F. used. Heat exchange could also be accomplished by injecting
Unit Ops
an inert heat exchange fluid (such as silicone oil) into the
expander and/or compressor as opposed to the external heat
T(F) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source exchangers discussed herein.
1 70 2OO A. -61.3 Air Example 5
70 856 B 47.6 +56.2 Comp Heat
3 70 856 C -56.2 System
Process Simulation No. 3
Hads 85.5 kJ/sec
RTE O.74 0235 Another exemplary process was simulated using the
8.3 kJ/mol computer Software package described above. The following
assumptions were made: 1) All streams can be heated or
cooled to 80° F. from the atmosphere, whether heating or
US 2015/0020993 A1 Jan. 22, 2015
cooling. All phase change energy is Supplied from the atmo Example 6
sphere. Energy to run the air blowers is neglected. 2) Working
fluid (CO) liquid inlet condition is set at 70° F., where the Use of Air as Working Fluid and Half-Systems
fluid is a liquidat its vapor pressure. 3) Pressure is set between
200-856 psia. 4) Desorption conditions not accounted for— 0237. One issue with conventional compressed air energy
assumed to happen at any T. Pset. No pressure or temperature storage is the low energy density of the compressed gas.
swing has been included. 5) Work is calculated as isentropic. However, Zeolite type absorbents will absorb air and have
6) Assumed inefficiencies based mechanical losses (BNI)— acceptable delta G values. Ifair were to be compressed into an
98% for expansion, 96% for compression. Lost energy is not insulated tank of Zeolites, and then simply discharged to the
accounted for in the simulation. 7) RTE is calculated as the atmosphere (no absorption on discharge) this would increase
power produced during piston expansion divided by the both the RTE of compressed air energy storage as well as the
power required by the piston compression. energy density.
0236 A schematic of the process used for the simulation is 0238. This would operate conceptually as a half-system
shown in FIGS. 3 and 4 for recharge and discharge, respec with only a single storage tank and that is not a closed cycle.
tively. Process conditions and the resulting RTE are shown in However, it is an improvement over ordinary CAES. Both the
Table 4, below. A CO model was used to model the working heat of compression and the absorption energy will be stored
fluid for the simulation. and available for discharge. Although activated carbon also
absorbs air, there should be a warning that high pressure air
TABLE 4 could ignite certain carbons and this would be a limit on those
particular absorbents.
Carbon Dioxide - Isentropic, Single Stage.
Discharge Sorption T = 210 F.
Example 7
Streams Unit Ops
Three-Loop Carbon Dioxide and Aqueous Ammonia
T(F) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source System
1 70 856 A. +68.5 Air
2 8O 856 B 31.0 0239. The absorption of carbon dioxide in aqueous ammo
3 150 856 C +17.7 Air nia Solution leads to a number of products including ammo
4 4.1 2OO D +28.5 System nium carbamate, bicarbonate, and carbonate. The ratio of
5
6
8O
2OO
2OO
2OO
E
F
+2.4
+43.8
System
System
these reaction products are a function of the carbon dioxide
loading, Solution pH, and the concentration of ammonia in the
Recharge aqueous media.
Desorption T = 70 F. Unit Ops 0240 Simplified chemical equations representing these
reactions include:
T(F) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source
NHCOONH-HO6 NH, HCO+NH
1 70 2OO A. -68.6 Air AH=8.06 kJ/mol (9)
2 286 856 B 40.7
3 8O 856 C
4 70 856 D -68.9 System
Hads 68.9 kJsec 6.7 kJ/mol Heat from Absorber NHHCO3,
kJ/mol
NH3+CO-H2O AH-64.26 (11)
RTE O.76
Carbon Dioxide - Isentropic, Two-Stage NHCOONHS

kJ/mol
2NH+COAH,-72.32 (12)
Expansion. Three-Stage Compression
Discharge Sorption T = 210 F. (NH4)2CO3, 2NH3+CO2+H2O AH-101.
22 kJ/mol (13)
Streams Unit Ops
0241 The schematic flow diagram for the process is
T(F) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source shown in FIG. 13.
1 70 856 A. +68.5 Air 0242. The operating parameters for the initial feasibility
2 8O 856 B 35.8 System evaluation are:
3 150 856 C +17.7 Air
4 102.5 2OO D +28.5 System 0243 1) Absorption vessel conditions are 150°F, and 257
5 8O 2OO E +2.4 System psi (-66° C. and 1.77 Mpa):
6 2OO 2OO F +43.8 System 0244 2) Desorption vessel conditions are 180° F. and 257
Recharge psi (-82°C.);
Desorption T = 70 F. Unit Ops 0245 3) Ammonia concentration level of 36% was main
tained;
T(F) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source 0246, 4) Total flow rate of working fluid equal to 142.6
1 70 2OO A. -68.7 Air kg/s;
2
3
135.8
8O
856
856
B
C
39.5 -38.0 System 0247 5) Expansion efficiency: 88%;
4 70 856 D -23.2 System 0248 6) Compressor efficiency: 84%;
Hads 79.6 kJsec 7.7 kJ/mol Heat from absorber
0249 7) Heat exchanger efficiency: 2%;
RTE O.906 0250) 8) The molar ratios of carbon dioxide to ammonia in
solution are between 0.35 to 0.60;
(0251 9) The reversible heat of reaction: 80 kJ/mol; and
US 2015/0020993 A1 Jan. 22, 2015
17
0252) 10) Thermodynamic and transport properties esti TABLE 7

mated with using the National Institute of Standards and Multi-Stage Compressors.
Technology (NIST) standard reference program.
0253 All state functions, for each location, as shown in Compression Heat
FIG. 13 are shown in Table 5. Stages Work, kJ/kg CO2 Exchangers QkJ/kg CO2
C1 20.90 H4 -53.79
TABLE 5 C2 21.36 H5 -31.13
C3 1989 H6 -34.62
C4 20.40
Physical parameters data at various locations.
Temperature Pressure Density Enthalpy Entropy Total: 82.55 -119.54
Location ( K) (Mpa) (kg/m) (kJ/kg) (kJ/kg K)
901 333.15 6.63 143.66 476.09 19083 3 Compression stages C1, C2, C3, C4 and C5 are shown in FIG, 13.
903 333.15 3.76 69.441 506.26 2.0852
904 299.82 2.3442 47.2O2 484.33 2.0935 Estimation of Sensible Heat:
905 333.15 2.32 40.213 S18.9 2.2043
0256
906 298.71 1.77 34.596 489.59 2.1581
915 305.37 2.28 44.562 490.84 2.1.193
0257 The sensible heat is defined as the amount of energy
916 333.71 3.17 56.84 S12.2 2.1311 required to raise the temperature of the solution to the tem
917 305.37 3.14 64.921 481.07 2.0351 perature of regeneration, which while not recovered in this
918 333.15 4.316 81.984 SOO.96 2.0469
919 305.37 4.275 96.472 466.34 1.94O1
flow chart, may allow for partial recovery. Assuming 36% by
920 334.26 5.9 120.76 486.74 1.9568 weight of ammonia concentration in water and maintaining
921 358.71 2.31 36.386 544.63 2.2795 the molar ratio of carbon dioxide to ammonia in the Solution
934 333.15 1.74 29.28 523.73 2.2703
934(1)* 333.15 1.74
between 0.35 to 0.6 during absorption and desorption cycle,
937 333.15 1.77 30.01 S23.41 2.2653 the reaction heat is:
940 339.93 6.63 136.34 486.23 19384
941 355.37 1.73 27.09 S45.31 2.333 (92,+9esia). 2-(122.95+119.54)/2–121.3
kJ/kg CO2
942 352.59 1.73 27.339 S42.61 2.3254
943(1)* 330.37 1.77
945(1)* 355.37 1.73
Since the total AQ for desorption and absorption is essentially
946(1)* 352.59 1.73 equal.
Locations are shown in FIG. 13. 0258 Accepting reaction heat 80 kJ/mol, as reported in the
Assuming that heat capacity (C) of the solution (both rich and lean) containing CO2/NHy literature
H2O is equal to 1 callig C,
80x (1000x0.36) (0.6-0.35), 17=424 kJ/kg of solution
0254 All calculations and thermodynamic state function
are normalized to 1 kg of carbon dioxide of working fluid. The The AT is the temperature difference between stream 43 and
reboiler 180-135° F =25° C.
assumed value for heat capacity (C), for the carbon dioxide/
ammonia/water Solution is equal to 1 cal/g C. The assumed 0259 Sensible (Qseasible) heat is equal to
density for the carbon dioxide?ammonia/water solution is
equal to 1 g/cm. The sensible heat requirements: 29.9 kJ/kg Q (121.3x25x4.18),424–29.9 kJ/kg CO2
carbon dioxide and stripping heat is Zero. 0260. The system Efficiency:
0255. The value for each expansion and compression work Efficiency (RTE)=(Work out)/(Work in +Sensible
is calculated as follows: E1 is calculated by referring to Table Heat)x100
5 above and FIG.13; subtracting the H (enthalpy) of the noted
output numbers corresponding to each device on the flow RTE=75.65/(82.55+29.9)x100–67.2%
diagram (line 9, Table 5) from the H (enthalpy) of the input
(line 1, Table 5). Thus, the value for E1 is 451.7-476.09–24. Example 8
39. Similarly, the values for multi-stage expanders (E1, E2
and E3) and multi-stage compressors are shown in Tables 6
and 7. Process Simulation No. 4
TABLE 6 0261 The system illustrated in FIG. 15 was simulated

Multi-Stage Expanders.
using ASPEN modeling software. This simulation is indepen
dent of the absorbent and employs CO as the working fluid.
Expansion Heat
Stages' Work, kJ/kg CO2 Exchangers QkJ/kg CO2 0262 This simulation calculates the thermodynamic effi
ciency of CO working fluid as it completes a full charge
E1 -24:39 H1 54.56
E2 -21.93 H2 34.57 discharge cycle. Note that this simulation does not show a
E3 -29.31 H3 33.82 specific absorption reaction. It assumes that heat is put into a
Total -75.65 122.9S
given reaction during charging/compression and withdrawn
from the reverse of that reaction during the discharge/expan
Expansion stages E1, E2 and E3 are shown in FIG, 13. sion thru the heat exchangers. The data generated in this
simulation is presented in Tables 8-15, below.
US 2015/0020993 A1 Jan. 22, 2015
TABLE 8 TABLE 10-continued

Expander Efficiency: 85%, Compressor Effic.: 84% Expander Efficiency: 85%, Compressor Effic.: 84%
Different Compressor Temperature Out. Different Compressor Temperature Out.
E30(P) = C10(P); C40(T, P) = E10(T, P): E30(T) NOT = C10(T) E30(P) = C10(P); C40(T, P) = E10(T, P): E30(T) NOT = C10(T)
Final Heater Final Cooler
Final Pr. Temp Temp Power Final Pr. Temp Temp Power
Out Out Out MW Out Out Out MW
E10 3S.OO 72.17 110 2.81 E10 in TP: C10 12.25 101 64 S.48 C10 in TP:
E20 1S.OO 51.2O 1OO 4.38 115 deg C./61 bar C2O 1943 104.5 62 3.49 37 deg C./5.8 bar
C30 33.89 112 61 4.10
E30 6.OO 41.60 4.8O
C40 61.39 117 4.12
11.99
17.20
TRUERTE 71.42
Final Cooler
Final Pr. Temp Temp Power
Out Out Out MW
TABLE 11
C10 14.94 100 69 6.90 C10 in TP:
C2O 21.03 100 62 2.58 18 deg C./5.6 bar Expander Efficiency: 85%, Compressor Effic.: 84%
C30 35.46 110 63 3.82 Different Compressor Temperature Out.
C40 61.51 115 3.81 E30(P) = C10(P); C40(T, P) = E10(T, P): E30(T) NOT = C10(T)
Final Heater
17.12
TRUERTE 70.06 Out Out Out MW
E10 35.00 72.17 110 2.81 E10 in TP:

E20 1S.OO 51.2O 1OO 4.38 115 deg C./61 bar
TABLE 9 E30 6.OO 41.60 4.8O
Expander Efficiency: 85%, Compressor Effic.: 84% 11.99

Different Compressor Temperature Out.
E30(P) = C10(P); C40(T, P) = E10(T, P): E30(T) NOT = C10(T) Final Cooler
Final Heater Out Out Out MW
Out Out Out MW C10 12.70 102 69 5.73 C10 in TP:
C2O 2O.O1 105 62 3.45 35 deg C./5.8 bar
E10 3S.OO 72.17 110 2.81 E10 in TP: C30 34.13 111 63 3.93
E20 1S.OO 51.2O 1OO 4.38 115 deg C./61 bar C40 61.2O 116 4.04
E30 6.OO 41.60 4.8O
17.15
11.99 TRUERTE 69.94
Final Cooler
Out Out Out MW TABLE 12
C10 13.80 103 69 6.38 C10 in TP:
Expander Efficiency: 85%, Compressor Effic.: 84%
C2O 21.02 103 62 3.17 28 deg C./5.7 bar Different Compressor Temperature Out.
C30 35.44 110 63 3.82
C40 61.47 115 3.81 E30(P) = C10(P); C40(T, P) = E10(T, P): E30(T) NOT = C10(T)
Final Heater
17.19 Final Pr. Temp Temp Power
TRUERTE 69.78 Out Out Out MW
E10 35.00 77.01 120 2.87 E10 in TP:

E20 1S.OO 6049 105 4.53 120 deg C./61 bar
TABLE 10 E30 6.OO 46.12 4.88
Expander Efficiency: 85%, Compressor Effic.: 84% 12.28

Different Compressor Temperature Out.
E30(P) = C10(P); C40(T, P) = E10(T, P): E30(T) NOT = C10(T) Final Cooler
Final Heater Out Out Out MW
Out Out Out MW C10 12.48 102 64 S.S8 C10 in TP:
C2O 1968 105 62 3.54 35 deg C./5.7 bar
E10 3S.OO 77.01 120 2.87 E10 in TP: C30 33.57 111 61 4.10
E20 1S.OO 6049 105 4.53 120 deg C./61 bar C40 61.10 116 4.12
E30 6.OO 46.12 4.88
17.33
12.28 TRUERTE 70.85
US 2015/0020993 A1 Jan. 22, 2015
19
TABLE 13
Mass Stol Ideal Vaport Molar
Pressure Flow Liq Vol Phase Enthalpy
Location bar Temp. C. kg's Flow m3/h Fraction kJ/kgmole
921 14.93721229 100 OO 436.186SO66 -391267.OO48
915 14.93721229 69 OO 436.186SO66 -392S86.3377
916 21.03372O89 100 OO 436.186SO66 -391449.4834
917 21.03372O89 62 OO 436.186SO66 -39311 14838
918 35.463.39734 110 OO 436.186SO66 -391429.8615
919 35.463.39734 63 OO 436.186SO66 -393637.51
940 6151466519 115 OO 436.186SO66 -39 1959.84.95
934 S.6 18 OO 436.186SO66 -3943O3.7714
909 35 72.1652OS6 OO 436.186SO66 -393.181881.8
903 35 10 OO 436.186SO66 -391416.2255
904 15 51.19538871 OO 436.186SO66 -393.342.6754
905 15 OO OO 436.186SO66 -391268.8689
906 6 41.6O482521 OO 436.186SO66 -393382.2592
941-2 61 22 OO 436.186SO66 O -4.04.047.2745
900 61 15 OO 436.186SO66 -391944.4882
941 6151466519 22 OO 436.186SO66 O -404077.447
TABLE 1.4 Other Embodiments

Hx40 HxSO Hx60 Hx7O 0263 All publications and patents referred to in this dis
Duty kJ/h) 107921 63.03 13595187.4 18058597.24 9.9E-07
closure are incorporated
-
herein by reference to the same
Pressure Drop O O O O eXtent as if each individual publication or patent application
kPa) were specifically and individually indicated to be incorpo
rated by reference. Should the meaning of the terms in any of
the patents or publications incorporated by reference conflict
TABLE 1.5
C10 C2O C30 C40
Compressor Speed rpm

Power kW) 6900.221073 2583.19.0312 3821.O2624 38.12.02
Capacity (act feed vol flow) 34174.65632 14743.26663 9951.324,512 5550.81
ACT m3/h)
Adiabatic Efficiency 84 84 84 84
Polytropic Efficiency 85.57 271157 84.58712734 84.90616828 84.988
Compressor Volume m3 O O O O
Delta TC) 82 31 48 52
Delta P kPa) 933.7212287 609.6SO8608 1442.967645 2605.13
Polytropic Head m 6021.124725 2228.1273.63 33O8.2S2O24 3303.64
Adiabatic Head m S910.464533 2212.661675 3272.944,422 3265.23
Dynamic Headm 6021.124725 2228.1273.63 33O8.2S2O24 3303.64
Polytropic Fluid Head kJ/kg) 59.047O6278 21.8SO4652 32.44286971 32.3976
Adiabatic Fluid Head kJ/kg) 57.961857O1 21.69879862 32.09662O41 32.021
Dynamic Fluid Head kJ/kg) 59.047O6278 21.8SO4652 32.44286971 32.3976
Polytropic Head Factor 1.OOO68214 1.OOOO2664 O.9998482OS O.999.13
Polytropic Exponent 1.327392O38 1.328738561 1.3339837O6 1.36064
Sentropic Exponent 1.266OO2311 1.261.753035 1.266416427 1.2885
Dynamic Delta P
RC-Typical Design Speed
RC-Volumetric Efficiency
PD Number of Cylinders O O O O
PD Borem
PD Stroke m)
PD Piston Rod Diameterm
PD Const Volmetric Efficiency
Loss %
Transient Rotational Power O O O O
kW)
Friction Loss Power kW O O O O
Fluid Power kW) 6900.221073 2583.19.0312 3821.O2624 38.12.02
Total Rotor Torque N-m
Transient Rotational Torque
N-m
Friction Loss Torque N-m)
Fluid Torque N-m
Duty kJ/h) 2484O795.86 929948S.123 137SS694.46 14E--O7
US 2015/0020993 A1 Jan. 22, 2015
20
with the meaning of the terms used in this disclosure, the 18. A method of charging and discharging an energy stor
meaning of the terms in this disclosure are intended to be age system comprising:
controlling. Furthermore, the foregoing discussion discloses charging the System comprising:
and describes merely example embodiments of the present providing an absorbent storage tank containing a work
invention. One skilled in the art will readily recognize from ing fluid that is chemically absorbed by an absorbent;
Such discussion and from the accompanying drawings and desorbing the working fluid from the absorbent in an
claims, that various changes, modifications and variations can endothermic process;
be made therein without departing from the spirit and scope of condensing the working fluid in an exothermic process
the invention as defined in the following claims. and transferring the condensed working fluid to a
1. A method for storing energy comprising: working fluid reservoir under pressure; and
providing an absorbent reservoir containing a working recycling heat generated during the condensing step to
fluid that is chemically absorbed by an absorbent; drive the desorbing step; and
desorbing the working fluid from the absorbent in an endot storing the working fluid in a working fluid reservoir
hermic process; and under pressure; and
condensing the working fluid in an exothermic process and discharging the system comprising:
transferring the condensed working fluid to a working expanding the working fluid;
fluid reservoir under pressure; chemically absorbing the working fluid with the absor
wherein at least some of the heat generated during the bent in the absorbent storage tank in an exothermic
condensing step is recycled to drive the desorbing step. process;
2. The method of claim 1, wherein the working fluid com recycling heat generated during the absorption reaction
prises carbon dioxide, ammonia, nitrous oxide, air, or water. to drive the expanding step; and
3. The method of claim 2, wherein the working fluid com storing the absorbent and the absorbed working fluid in
prises carbon dioxide or ammonia. the absorbent storage tank.
4. The method of claim3, wherein the absorbent comprises 19-35. (canceled)
an organic amine, an inorganic base, an activated carbon, 36. An energy storage system comprising:
silica gel, a Zeolite, a metal organic framework, or any com a working fluid reservoir containing compressed working
bination thereof. fluid;
5. The method of claim 4, wherein the absorbent comprises an expander that fluidly communicates with the working
an organic amine selected from monoethanolamine, pipera fluid reservoir and is configured to expand the working
Zine, ammonia, morpholine, diethanolamine, diglycolamine, fluid;
diisopropanolamine, triethanolamine, dibutylamine, methyl an absorbent reservoir containing an absorbent, wherein
diethanolamine, diethylenetriamine, or any combination the absorbent reservoir fluidly communicates with the
thereof. expander and is configured to receive and absorb the
6. The method of claim 2, wherein the working fluid com expanded working fluid;
prises ammonia. a first heat exchanger that thermally communicates with
7. The method of claim 6, wherein the absorbent comprises the absorbent reservoir and is configured to transfer heat
a metal halide salt, a mild acid, water, activated carbon, silica generated by the absorption of the working fluid by the
gel, a Zeolite, or metal organic framework. absorbent to the working fluid during the discharge of
8. The method of claim 2, wherein the working fluid com the system;
prises nitrous oxide. a pressure release mechanism configured to reduce pres
9. The method of claim8, wherein the absorbent comprises sure in the absorbent reservoir; and
a food oil, silicone oil, activated carbon, silica gel, Zeolite, or a compressor that fluidly communicates with the absorbent
metal organic framework. reservoir and fluidly communicates with the working
10. The method of claim 1, wherein the heat generated fluid reservoir and is configured to compress the work
from the condensing step is recycled to drive the desorbing ing fluid that desorbs from the absorbent; and
step using a heat exchanger. a second heat exchanger in thermal communication with
11. The method of claim 1, further comprising compress the working fluid in the compressor, in thermal commu
ing the working fluid using a reversible turbine. nication with the absorbent and working fluid in the
12. The method of claim 1, further comprising compress absorbent storage tank, and configured to transfer heat
ing the working fluid and storing the working fluid in the that is generated by the compression of the working
working fluid reservoir in a liquid State, a critical state, or a fluid, to the absorbent and working fluid in the absorbent
trans-critical state. reservoir.
13. The method of claim 1, wherein the working fluid is 37. The system of claim 36, wherein the working fluid
compressed to and stored at a pressure of from about 1 bar to comprises carbon dioxide, ammonia, nitrous oxide, air, or
about 100 bar. Water.
14. The method of claim 11, further comprising a second 38. The system of claim 37, wherein the working fluid
compression stage after the first compression. comprises carbon dioxide.
15. The method of claim 1, wherein the working fluid is 39. The system of claim 38, wherein the absorbent com
expanded to a pressure of from about 0.1 bar to 10 bar. prises an organic amine, inorganic base, activated carbon,
16. The method of claim 1, wherein the working fluid is silica gel, Zeolite, or metal organic framework.
stored at ambient temperature. 40. The system of claim 39, wherein the absorbent com
17. The method of claim 1, further comprising heating the prises an organic amine selected from monoethanolamine,
working fluid prior to expansion using an outside heat source. piperazine, ammonia, morpholine, diethanolamine, diglyco
US 2015/0020993 A1 Jan. 22, 2015
lamine, diisopropanolamine, triethanolamine, dibutylamine, 52. The system of claim 36, wherein the first heat
methyl-diethanolamine, or diethylenetriamine. exchanger and second heat exchanger each comprise high
41. The system of claim 37, wherein the working fluid surface area fin-shaped structures within the absorbent stor
comprises ammonia. age tank.
42. The system of claim 41, wherein the absorbent com 53. The system of claim 36, further comprising one or more
additional compressors, fluidly connected to and positioned
prises a metal halide salt, mild acid, water, activated carbon, between the first compressor and the working fluid storage
silica gel, Zeolite, or metal organic framework. tank.
43. The system of claim 37, wherein the working fluid 54. The system of claim 36, further comprising one or more
comprises nitrous oxide. additional expanders, fluidly connected to and positioned
44. The system of claim 43, wherein the absorbent com between the first expander and the absorbent storage tank.
prises a food oil, silicone oil, activated carbon, silica gel. 55. The system of claim 36, wherein the pressure release
Zeolite, or metal organic framework. mechanism is a valve.
45. The system of claim 36, wherein the compressor and 56. The system of claim 36, further comprising a pump and
expander comprise a reversible turbine. a sprayer that each fluidly communicates with each other and
with the absorbent storage tank, wherein the pump pumps the
46. The system of claim 36, wherein the compressor com absorbent and absorbed working fluid to the sprayer and the
prises a turbine, piston, radial reaction turbine. sprayer sprays the fluid into the absorbent storage tank.
47. The system of claim 36, wherein the expander com 57. The system of claim 56, wherein the sprayer sprays the
prises a turbine, piston, or turbo-expander. absorbent over a heat exchanger with high Surface area fin
48. The system of claim 36, further comprising an electri shaped structures within the absorbent storage tank.
cal generator connected to the expander. 58. The system of claim 36, further comprising a separator
that fluidly communicates with the absorbent storage tank
49. The system of claim 36, further comprising a motor and the compressor.
connected to the compressor. 59. The system of claim 58, wherein the separator is a
50. The system of claim 36, further comprising an external centrifugal or cyclonic separator.
heat source, in thermal communication with the expanded 60. The system of claim 58, wherein the separator is a
working fluid. demister or a filter.
51. (canceled)

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(TIL| |(1| |(L| |

105 OMEA (exp, 40C) - - - -- -- -- - --- - - - - Y - - - - - - a raw- - - - - - - - V - - - - - as - - - - -

AMEA (exp, 40C)

n 10 ele - --- ---- - - - - -- -- - - -- -- --a- ----- ---- - - --

O 0.2 0.4 0.6 0.8 1

Throttle & Discharge

EXPANSION & ABSORPTION

oro FIG. 15A

DESORPTION & COMPRESSION

-20 30 80 130 180

MECHANCAL-CHEMICAL ENERGY stored energy is only recovered if it is also desired to burn

TABLE 1-continued TABLE 1-continued

Tetrabutylammonium 2OO Pentaglycerin 192 81

Carbon Dioxide - Isentropic, Two-Stage NHCOONHS

0252) 10) Thermodynamic and transport properties esti TABLE 7

TABLE 6 0261 The system illustrated in FIG. 15 was simulated

TABLE 8 TABLE 10-continued

E10 35.00 72.17 110 2.81 E10 in TP:

Expander Efficiency: 85%, Compressor Effic.: 84% 11.99

E10 35.00 77.01 120 2.87 E10 in TP:

Expander Efficiency: 85%, Compressor Effic.: 84% 12.28

TABLE 1.4 Other Embodiments

Compressor Speed rpm

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